Gold(I)-Catalyzed Intramolecular Oxidation ... · 5 2.2 The Control Experiments Regarding Acid...

Supporting Information

Gold(I)-Catalyzed Intramolecular Oxidation-Cyclopropanation Sequence of Enynes:

A Convenient Access to [n.1.0]Bicycloalkanes

Deyun Qian, a Junliang Zhang*a,b

a Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry,

East China Normal University, 3663 N, Zhongshan Road, Shanghai 200062 (P. R. China), Fax: (+86)

21-6223-5039; E-mail: [email protected]

b State key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese

Academy of Sciences.

Fax:(+86)-021-6223-5039; e-mail : [email protected]

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

2

Content

1. General ............................................................................................................................................... 3

2. Experimental Procedures and Characterization Data .................................................................. 3

2.1 Optimization of Reaction Conditions ............................................................................................... 3

2.2 The Control Experiments Regarding Acid Stability ....................................................................... 5

2. 3 General Procedure for Synthesis of Enyne Substrates 1 ............................................................... 6

2.3.1 Preparation of Enyne Substrates 1b to 1i ...................................................................................... 6

2.3.2 Preparation of Enyne Substrates 1j and 1k .................................................................................. 7

2.3.3 Preparation of Enyne Substrates 1l to 1n ...................................................................................... 8

2.3.4 Preparation of Enyne Substrates 1o to 1q ................................................................................... 10

2.4 General Procedure for Gold(I)-Catalyzed Intramolecular Oxidation-Cyclopropanation Sequence of Enynes 1 ............................................................................................................................. 12

General Procedure A .............................................................................................................................. 12

General Procedure B .............................................................................................................................. 16

2.5 Gold(I)-Catalyzed Reaction of Enyne 1a ........................................................................................ 21

2.6 Gold(I)-Catalyzed Reaction of Enyne 1r ........................................................................................ 22

2.7 Crystal Structure of Bicyclo [3.1.0]hexan-2one 3f .................................................................... 23

3. References ........................................................................................................................................ 24

4. 1H and 13C NMR Spectra for New Compounds ............................................................................... 25


3

1. General

All air- and moisture-sensitive manipulations were carried out with standard Schlenk techniques under

nitrogen or in a glove box under nitrogen. 1H NMR, 13C NMR spectra were measured at 400 MHz and

100 MHz in CDCl3. Data for 1H NMR spectra are reported as follows: chemical shift (ppm, referenced

to TMS; s = singlet, d = doublet, t = triplet, dd = doublet of doublets, dt = doublet of triplets, m =

multiplet), coupling constant (Hz), and integration. Data for 13C NMR are reported in terms of chemical

shift (ppm) relative to residual solvent peak (CDCl3: 77.0 ppm). Tetrahydrofuran, benzene and toluene

were distilled from sodium and benzophenone prior to use. Dichloromethane and 1,2-dichloroethane

(DCE) was distilled from CaH2 prior to use.

2. Experimental Procedures and Characterization Data

2.1 Optimization of Reaction Conditions:


4

Table S1 Optimization of Reaction Conditionsa

Entry Catalyst R Additive

(eq.)

Solvent/

Time (h)

Yield

(3b/1b/4 %)b

1 [Ph3PACl]/[AgNTf2] H - DCE/12 13/88/0

2 [Ph3PACl]/[AgNTf2] H MsOH (1.2) DCE/12 22/83/0

3 c [IPrACl]/[AgNTf2] H MsOH (1.2) DCE/12 complicated mixture

4 [IPrACl]/[AgNTf2] 2-Br - DCE/21 60/30/5

5 [IPrACl]/[AgNTf2] 2-Br MsOH (1.2) DCE/21 67/14/5

6 [IPrACl]/[AgNTf2] 2-Br HNTf2 (1.2) DCE/21 68/11/10

7 [IPrACl]/[AgNTf2] 2-Br MsOH (1.2) DCE/36 59/13/ 9

8 d [L1AuCl] /[AgNTf2] 2-Br MsOH (1.2) DCE/21 35/19/30

9 e [L2AuCl] /[AgNTf2] 2-Br MsOH (1.2) DCE/21 31/22/31

10 [IPrACl]/[AgNTf2] 4-Ac MsOH (1.2) DCE/21 63/30/0

11 [IPrACl]/[AgSbF6] 4-Ac MsOH (1.2) DCE/21 52/24/0

12 [IPrACl]/[AgNTf2] 4-Ac HNTf2 (1.2) DCE/21 64/32/0

13 [IPrACl]/[AgNTf2] 4-Ac HOAc (1 mL) DCE/28 63/29/0

14f [IPrACl]/[AgNTf2] 4-Ac HNTf2 (1.2) DCE/21 62/20/0

15g [IPrACl]/[AgNTf2] 4-Ac HNTf2 (1.2) DCE/36 73/26/0

16h [IPrACl]/[AgNTf2] 4-Ac HNTf2 (1.2) DCE/36 81/12/0

17 i [IPrACl]/[AgNTf2] 4-Ac HNTf2 (1.2) DCE/36 66/31/0

18 [IPrACl]/[AgNTf2] 4-Ac MsOH (1.2) THF/21 41/53/0

19 [IPrACl]/[AgNTf2] 4-Ac MsOH (1.2) CH3CN/21 45/51/0

20 - 4-Ac MsOH (1.2) DCE/21 nr

21 [AgNTf2] 4-Ac MsOH (1.2) DCE/21 23/74/0

22 Rh2(OAc)4 2-Br - toluene/21 12/53/32

23 PtCl2 2-Br - DCE/21 nr

24 Pd(OAc)2 4-Ac MsOH (1.2) DCE/21 nr

a The reaction was performed with 0.2 mmol of 1a and 5 mol% of catalyst in 2.0 mL DCE at 60 oC, Au/AgNTf2 =

1:1. b Determined by 1H NMR analysis using CH2Br2 as the internal reference. c IPr = N,N’-bis(2,6-

diisopropylphenyl)imidazol-2-ylidene. d L1 = X-phos. e L2 = P(tBu)2(o-biphenyl). f 1.2 eq. of oxidant. g 71% isolated

yield. h 10 mol% of catalyst. i 3.0 eq. of oxidant.


5

2.2 The Control Experiments Regarding Acid Stability:

(1)

Entry Acid 3d (mmol)

t = 0 h

The yield of 3d (%)a

t = 2 h

A - 0.1 96

B MsOH 0.1 46

C HNTf2 0.1 0

a Determined by 1H NMR analysis using CH2Br2 as the internal reference.

In three dried glass tube, the corresponding acid (1.2 eq.) in DCE (0.5 mL) was added respectively to a

solution of 3d (0.1 mmol) in DCE (o.5 mL) at room temperature under nitrogen. The reaction mixture

was stirred at 60 °C in the same oil and the progress of the reaction was monitored by TLC. After 2h,

the reaction was treated with saturated aqueous NaHCO3 (5 mL), and the resulting mixture was

extracted with DCM (3 × 5 mL). The combined organic layers were dried with anhydrous Na2SO4. The

mixture was concentrated and the crude yield was determined by 1H NMR.

(2)

Entry R Acid Time (h) Yield (%)a

1 Me MsOH 38 62

2 Me HNTf2 38 41

3 MeO MsOH 48 81

4 MeO HNTf2 48 65

a Determined by 1H NMR analysis using CH2Br2 as the internal reference.

3d

NTs

O

O

MeO

acid (1.2 eq.)DCE, 60 oC, 2 h

A B C


6

2. 3 General Procedure for Synthesis of Enyne Substrates 1:

2.3.1 Preparation of Enyne Substrates 1b to 1i:

R COOH

1. TsCNO (1.0 eq.)NEt3 (1.0 eq.)THF, rt, 1 h

O NTs

R

2. NEt3 (3.0 eq.)Allylic Bromide (3.0 eq.)THF, rt, 12 h

In a flame dried round-bottom flask, the corresponding carboxylic acid (5.0 mmol) was dissolved in dry

THF (0.5 M) under argon and tosyl isocyanate (1.0 equiv) was added to the solution. After being stirred at rt

for 10 mins under the inter N2 was disconnected and Et3N (1.0 equiv) was added drop-wise to the open flask,

allowing the release of the formed CO2. After being stirredg for 1h at rt, allyl bromide (3.0 equiv) and extra

Et3N (3.0 equiv) were sequentially added and the mixture was stirred overnight. After the starting material

was consumpted completely, the solvent was removed under vacuum. The residue was purified by column

chromatography on silica gel (hexanes/EtOAc = 5:1) to afford the corresponding enyne products. The

spectra of 1b1, 1c3, 1f4 and 1i1

are consistened with the literatures.

Substrate 1d

1H NMR (400 MHz, CDCl3): 7.92 (d, δ J = 7.6 Hz, 2H), 7.48-7.46 (m, 2H), 7.30 (d, J = 7.2 Hz, 2H), 7.00

(d, J = 7.6 Hz, 2H), 6.00-5.94 (m, 1H), 5.42 (d, J = 17.2 Hz, 1H), 5.31 (d, J = 10.0 Hz, 1H), 4.69 (d, J = 3.6

Hz, 2H), 3.83 (s, 3H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 161.8, 152.8, 145.0, 136.0, 134.7,

132.6, 129.4, 128.7, 118.8, 114.4, 111.1, 94.0, 81.2, 55.4, 49.4, 21.6; MS (EI): m/z (%) = 369 (M+, 6.54),

159 (100)；HRMS (EI): calculated for [C20H19NO4S]+ 369.1035, found: 369.1033.

Substrate 1e


7

1H NMR (400 MHz, CDCl3): δ 8.26 (d, J = 7.6 Hz, 1H), 7.95 (d, J = 6.4 Hz, 3H), 7.88 (d, J = 7.6 Hz, 1H),

7.78 (d, J = 6.8 Hz, 1H), 7.59 (t, J = 8.8 Hz, 2H), 7.47-7.44 (m, 1H), 7.28 (d, J = 7.6 Hz, 2H), 6.04-6.00 (m,

1H), 5.46 (d, J = 16.8 Hz, 1H), 5.35 (d, J = 10.0 Hz, 1H), 4.77 (s, 2H), 2.40 (s, 3H); 13C NMR (100 MHz,

CDCl3): 152.6, 145.1, 135.δ 9, 133.5, 133.0, 132.9, 131.7, 129.5, 128.7, 128.5, 127.8, 127.0, 127.9, 125.7,

125.1, 118.9, 117.0, 91.8, 86.0, 49.4, 21.6; MS (EI): m/z (%) = 389 (M+, 2.44), 179 (100)； HRMS (EI):

calculated for [C23H19NO3S]+ 389.1086, found: 389.1086.

Substrate 1g

E/Z = 4.2:1; 1H NMR (400 MHz, CDCl3): 7.9δ 1 (d, J = 6.8 Hz, 2H), 7.53 (d, J = 7.6 Hz, 2H), 7.48-7.45 (m,

1H), 7.40-7.37 (m, 2H), 7.30-7.27 (m, 2H), 5.90-5.88 (m, 0.8H), 5.75-5.72 (m, 0.2H), 5.64-5.60 (m, 0.8H),

5.55-5.49 (m, 0.2H), 4.76 (d, J = 6.0 Hz, 0.3H), 4.63 (d, J = 6.0 Hz, 1.6H), 2.42 (s, 3H), 1.82 (d, J = 6.8 Hz,

0.5H), 1.74 (d, J = 6.0 Hz, 2.4H); 13C NMR (100 MHz, CDCl3): δ 152.5, 144.9, 136.1, 134.7, 132.6, 131.0,

130.9, 129.4, 129.3, 128.6, 128.5, 125.3, 125.0, 119.5, 92.8, 81.6, 48.9, 44.2, 21.6, 17.6, 13.1. The

spectroscopic data match well with those in the literature.4

Substrate 1h

The enyne substrate 1h was synthesized according to literature procedure reported by Lu.5 The spectrum

of substrate 1h was consistened with the literature.3

2.3.2 Preparation of Enyne Substrates 1j and 1k:

Substrates 1j and 1k were synthesized following a published literature procedure.6


8

To a solution of allylamine (1.8 mL, 24.0 mmol) in a solvent mixture[MeOH (2 mL) + H2O (2 mL)]

was slowly added the corresponding propynoate (1.68 g, 20.0 mmol) at -20 °C to -30 °C with stirring.

After addition of the propynoate, the stirring was continued for 5 minutes. The solvent was evaporated

and column chromatography on silica gel (hexanes/EtOAc = 3:1) afforded the 2-alkynamides of

primary allylic amines. To a solution of 2-alkynamides of primary allylic amines (2.0 mmol) in THF (8

mL) was added NaH (128 mg, 60% in oil, 3.2 mmol) and CH3I (0.2 mL, 3.2 mmol). The mixture was

stirred for 30 min then poured into ice water (40 mL), extracted with CH2Cl2 (3 x 20 mL), washed

(brine), dried (Na2SO4) and evaporated the solvent. The residue was purified by column chromatography

on silica gel (hexanes) to afford corresponding enyne products. The spectrum of substrates 1j was

consistened with the literature.2

Substrate 1k

1H NMR (400 MHz, CDCl3): δ 7.50-7.46 (m, 2H), 6.88-6.86 (m, 2H), 5.87-5.71 (m, 1H), 5.27-5.18 (m,

2H), 4.25-4.23 (m, 1.2H), 4.07-4.06 (m, 0.8H), 3.82 (m, 3H), 3.21 (s, 1.2H), 2.97 (m, 1.8H); 13C NMR (100

MHz, CDCl3): δ 161.0, 154.9, 154.7, 134.1, 132.7, 132.1, 118.0, 117.8, 114.2, 112.4, 90.9, 90.3, 80.9, 80.7,

55.3, 53.7, 48.9, 35.8, 32.0; IR (neat): ν 3405, 3324, 3050, 2991, 2204, 1668, 1353, 1324, 1169, 1139,

1083, 928, 770 cm-1; HRMS (EI): calculated for [C14H15NO2]+ 229.1103, found: 229.1102.

2.3.3 Preparation of Enyne Substrates 1l to 1n:


9

Substrates 1l, 1m and 1n were synthesized following a published literature procedure.7

In a flame dried double Schlenk flask, a solution of the corresponding alkyne (20.0 mmol) in anhydrous

THF (20 mL) was cooled to -78 °C under an argon atmosphere and n-BuLi (2.5 M in hexane, 8.0 mL,

20.0 mmol) was added dropwise. The solution was stirred for 40 min, and then a solution of boron

trifluoride diethyl etherate (3.1 mL, 25.0 mmol) and ethyl pent-4-enoate (10.0 mmol) in anhydrous THF

(5.0 mL) was added. The slightly yellow reaction mixture was stirred for 30 min and the cooling device

was removed. A saturated aqueous solution of ammonium chloride (30 mL) was added and the aqueous

layer was extracted with diethyl ether (3 x 30 mL). The combined organic phases were washed with

brine (50 mL) and dried over Na2SO4. Removal of the solvent under reduced pressure led to a brown oil,

which was subjected to flash column chromatography on silica (hexanes/EtOAc = 50:1 to 20: 1). The

spectrum of substrates 1l was consistened with the literature.7

Substrate 1m

1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 7.6 Hz, 2H), 5.90-5.80 (m, 1H),

5.11-5.01(m, 2H), 3.83 (s, 3H), 2.77 (t, J = 7.6 Hz, 2H), 2.50-2.45 (m, 2H); 13C NMR (100 MHz, CDCl3):

δ 187.1, 161.6, 136.4, 135.4, 135.1, 115.6, 114.3, 111.7, 92.1, 87.6, 55.4, 44.4, 28.1; MS (EI): m/z (%)

= 214 (M+, 14.08), 159 (100)；HRMS (EI): calculated for [C14H14O2]+ 214.0994, found: 214.0945.

Substrate 1n


10

1n’ was synthesized following the procedure of the literature 8.

1n, 1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.4 Hz, 2H), 4.77 (s, 1H), 4.73

(s, 1H), 3.84 (s, 3H), 2.80 (t, J = 7.2 Hz, 2H), 2.44 (t, J = 7.2 Hz, 2H), 1.77 (m, 3H); 13C NMR (100 MHz,

CDCl3): δ 187.4, 161.6, 143.8, 135.1, 114.3, 111.7, 110.6, 92.1, 87.6, 55.4, 43.5, 31.8, 22.6; MS (EI):

m/z (%) = 228 (M+, 6.76), 159 (100)；HRMS (EI): calculated for [C15H16O2]+ 228.1150, found:

228.1149.

2.3.4 Preparation of Enyne Substrates 1o to 1q:

Substrate 1o

Ph

O

OH

MeNH(OMe)•HCl (2.5 eq.)CDI (1.2 eq.)

CH2Cl2, rt, 14 hPh

O

N

Me

OMe

1o'

Ph

O

OMe

Ph

O

N

Me

OMeOMe

n-BuLi (2.0 eq.)

THF, -78 oC, 1h

1o

1o''

1o''

Ph OH

OBr

LDA (2.0 eq.)

1o’, prepared by a procedure reported by Kim.9 Weinreb amide 1o’’, prepared according to the

literature.10

n-BuLi (2.5 M in hexane, 7.2 mL, 18.0 mmol) was added dropwise to a solution of 4-Ethynylanisole

(2.4 g, 18.0 mmol) in THF (10 mL) at –78 °C. The mixture was stirred for 30 min. The above solution

was transferred via cannula to the Weinreb amide 1o’’ (2.1 g, 9.0 mmol) in THF (10 mL) at –78 °C,

stirred for 1 h and let warm up to room temperature. Then, 1 N HCl was added dropwise until

disappearance of the white precipitate. The reaction mixture was extracted with Et2O (3 x 20 mL) and


11

the combined organic layers were washed with brine (30 mL). The organic layer was dried over Na2SO4

and concentrated under reduced pressure. The crude product was purified by FC (hexanes/EtOAc = 20:1)

to afford 1o (1.9 g, 70%). Yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.51 (d, J = 8.4 Hz, 2H), 7.30-

7.26 (m, 2H), 7.20-7.18 (m, 3H), 6.90 (d, J = 8.4 Hz, 2H), 5.84-5.74 (m, 1H), 5.13-5.06 (m, 2H), 3.84 (s,

3H), 3.16-3.11 (m, 1H), 3.05-2.99 (m, 1H), 2.88-2.83 (m, 1H), 2.57-2.50 (m, 1H), 2.43-2.36 (m, 1H); 13C

NMR (100 MHz, CDCl3): δ 190.1, 161.7, 138.9, 135.1, 134.8, 129.1, 128.5, 128.4, 128.3, 126.4, 117.5,

114.3, 111.7, 93.3, 87.3, 55.6, 55.4, 36.7, 35.1; MS (EI): m/z (%) = 304 (M+, 3.42), 159 (100)；HRMS

(EI): calculated for [C21H20O2]+ 304.1463, found: 304.1461.

Substrate 1p

1p, prepared by a modification of a produce reported by Narasaka.11

1p’, prepared according to the literature.12 A solution of 2-heptynal13 (1.10 g, 10.0 mmol) in THF was

added to a solution of but-3-enylmagnesium bromide (1M in THF, 15.0 mmol) at 0 °C and stirring was

continued for 1 h. The reaction was carefully quenched with water at 0 °C and the aqueous layer was

extracted with methyl tert-butyl ether. The combined organic phases were dried over Na2SO4 before

they were filtered and evaporated. This material was not purified, but rather used as a mixture in the

subsequent step.

In a dry flask under argon, to a dichloromethane solution (100 ml) of 1p’ was added pyridinium

dichromate (5.6 g, 15.0 mmol). The reaction mixture was stirred at rt for 48 h and filtered through

Celite. The filtrate was concentrated in vacuo and purification by flash column chromatography gave

the title compound 1p (1.10 g; 67% yield).

1H NMR (400 MHz, CDCl3): δ 5.85-5.75 (m, 1H), 5.06-4.98 (m, 2H), 2.64 (t, J = 7.2 Hz, 2H), 2.42-

2.34 (m, 4H), 1.59-1.52 (m, 2H), 1.45-1.40 (m, 2H), 0.93 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz,


12

CDCl3): δ 187.4, 136.4, 115.5, 94.6, 80.7, 44.5, 29.7, 28.0, 21.9, 18.6, 13.4; HRMS (EI): calculated

for [C11H16O]+ 164.1201, found: 164.1199.

Substrate 1q

To a solution of 3-phenylpropiolic acid (0.75 g, 5.0 mmol) in CH2Cl2 (10 mL), was added dropwise a

solution of DCC (1.03 g, 5.0 mmol) and DMAP (61.1 mg, 0.5 mmol) in CH2Cl2 (10 mL) at -20 °C. N-

benzylbut-3-en-1-amine14 ( 0.74 g, 4.6 mmol) in CH2C12 (5 mL) was then added and the mixture was

stirred for 20 h at room temperature. The solid was filtered off and the filtrate was washed with 0.1 N

HCI (10 mL) and dried (Na2SO4). After removal of the solvent, column chromatograph (hexanes/EtOAc

= 5: 1) gave the oily product 1q (1.20 g, 90 %).

1H NMR (400 MHz, CDCl3): 7.δ 55 (d, J = 7.2 Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.35-7.24 (m, 8H),

5.82-5.73 (m, 1H), 5.11-5.03 (m, 2H), 4.87 (s, 1H), 4.69 (s, 1H), 3.65 (t, J = 7.2 Hz, 1H), 3.45 (t, J = 7.2

Hz, 1H), 2.42-2.37 (m, 1H), 2.33-2.28 (m, 1H); 13C NMR (100 MHz, CDCl3) δ: 154.9, 154.7, 136.6,

136.4, 134.9, 134.3, 132.38, 132.35, 130.04, 130.00, 128.8, 128.7, 128.5, 128.4, 128.1, 127.9, 127.6,

127.5, 110.5, 120.4, 117.5, 117.0, 90.3, 90.1, 81.8, 81.7, 52.9, 47.8, 47.6, 43.8, 33.0, 31.6; MS (EI):

m/z (%) = 289 (M+, 1.43), 129 (100)；HRMS (EI): calculated for [C20H19NO]+ 289.1467, found:

289.1467.

2.4 General Procedure for Gold(I)-Catalyzed Intramolecular Oxidation-Cyclopropanation

Sequence of Enynes 1:

General Procedure A:


13

In a dried glass tube, a mixture of IPrAuCl (6.2 mg, 0.01 mmol, 5 mol %) and AgNTf2 (3.8 mg, 0.01

mmol, 5 mol %) in DCE (1 mL) was stirred at room temperature under nitrogen for 30 min to generate

the gold catalyst. 4-acetylpyridine N-oxide (54.8 mg, 0.4 mmol), MsOH (0.24 mmol) and the premixed

catalyst solution was added sequentially to a solution of enynes 1 (0.2 mmol) in DCE (1 mL) at room

temperature under nitrogen. After stirring at 60 °C for 1 – 72 h, the reaction was treated with saturated

aqueous NaHCO3 (5 mL), and the resulting mixture was extracted with DCM (3 × 5 mL). The

combined organic layers were dried with anhydrous Na2SO4. The mixture was concentrated and the

residue was purified by column chromatography on silica gel (hexanes/EtOAc = 5:1 to 7:3) to afford the

desired product 3.

1-benzoyl-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3b).

3bTsN

PhO

O

White solid, m. p. = 159-161 °C, 71% yield (hexanes/ethyl acetate = 7:3).

1H NMR (400 MHz, CDCl3): 7.9δ 0 (d, J = 7.2 Hz, 2H), 7.70 (d, J = 7.2 Hz, 2H), 7.55-7.52 (m, 1H),

7.34-7.33 (m, 4H), 4.09-4.02 (m, 2H), 2.55-2.53 (m, 1H), 2.46 (s, 3H), 2.00-1.97 (m, 1H), 1.36 (s, 1H);

13C NMR (100 MHz, CDCl3) δ: 192.2, 169.3, 145.4, 135.5, 134.5, 133.6, 129.8, 129.2, 128.3, 128.2,

47.3, 38.6, 21.7, 21.4, 19.2. The spectroscopic data match well with those in the literature.1

1-(4-methylbenzoyl)-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3c).


14

3cTsN

O

O

Me


m. p. = 1H NMR (400 MHz, CDCl3): 7.9δ 0 (d, J = 7.2 Hz, 2H), 7.60 (d, J = 7.2 Hz, 2H), 7.33 (d, J =

7.2 Hz, 2H), 7.12 (d, J = 7.2 Hz, 2H), 4.08-4.05 (m, 2H), 2.51 (s, 1H), 2.45 (s, 3H), 2.37 (s, 3H), 1.95 (s,

1H), 1.33 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 191.6, 169.4, 145.4, 144.5, 134.4, 132.9, 129.7,

129.4, 129.0, 128.1, 47.3, 38.5, 21.7, 21.6, 21.2, 19.0; IR (neat): ν 3091, 2960, 2855, 1731, 1672, 1604,

1357, 1171, 1105, 1084, 1002, 960, 810, 763, 713 cm-1; HRMS (ESI): calculated for [C20H19NNaO4S]+

392.09270, found:392.09233.

1-(4-methoxybenzoyl)-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3d).


1H NMR (400 MHz, CDCl3): 7.9δ 1 (d, J = 7.2 Hz, 2H), 7.74 (d, J = 7.6 Hz, 2H), 7.34 (d, J = 7.6 Hz,

2H), 6.83 (d, J = 7.6 Hz, 2H), 4.08-3.99 (m, 2H), 3.86 (s, 3H), 2.53-2.50 (m, 1H), 2.45 (s, 3H), 1.90 (t,

J = 5.8 Hz, 1H), 1.35-1.34 (m, 1H); 13C NMR (100 MHz, CDCl3) δ: 190.1, 169.5, 164.0, 145.4, 134.5,

131.8, 129.8, 128.3, 128.2, 113.7, 55.5, 47.3, 38.4, 21.7, 20.6, 19.2; IR (neat): ν 3101, 3017, 2935,

2903, 2838, 1723, 1670, 1596, 1379, 1350, 1258, 1162, 1115, 1094, 1028, 838, 808, 755 cm-1; HRMS

(ESI): calculated for [C20H19NNaO5S]+ 386.10567, found: 386.10567.

1-(1-naphthoyl)-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3e).


15

3eTsN

O

O


1H NMR (400 MHz, CDCl3): δ 8.27-8.26 (m, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.80 (d, J = 8.0 Hz, 3H),

7.59 (d, J = 6.8 Hz, 2H), 7.47-4.45 (m, 2H), 7.33-7.25 (m, 3H), 4.07 (s, 1H), 2.70 (s, 1H), 2.42 (s, 3H),

2.22 (s, 1H), 1.40 (s, 1H); 13C NMR (100 MHz, CDCl3) δ: 195.5, 168.8, 145.3, 134.5, 133.84, 133.78,

133.0, 130.2, 129.8, 128.60, 128.55, 128.0, 127.9, 126.5, 125.0, 124.1, 47.1, 40.1, 24.1, 21.7, 21.1; IR

(neat): ν 3096, 2919, 1727, 1672, 1623, 1357, 1303, 1172, 1118, 1099, 900, 813, 801, 768, 662 cm-1;

HRMS (ESI): calculated for [C23H19NNaO4S]+ 428.09270, found: 428.09245.

1-benzoyl-5-methyl-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3f).

3fTsN

PhO

O

Me


1H NMR (400 MHz, CDCl3): 7.9δ 2 (d, J = 7.2 Hz, 2H), 7.51-7.48 (m, 1H), 7.42 (d, J = 7.2 Hz, 2H),

7.36 (d, J = 7.2 Hz, 2H), 7.27-7.23 (m, 2H), 4.16 (d, J = 10.4 Hz, 2H), 3.92 (d, J = 10.4 Hz, 2H), 2.48

(s, 3H), 2.08 (s, 1H), 1.24 (s, 4H); 13C NMR (100 MHz, CDCl3) δ: 191.8, 170.5, 145.5, 136.4, 134.6,

133.3, 129.8, 128.6, 128.5, 128.2, 52.9, 43.4, 31.4, 22.7, 21.8, 15.7; IR (neat): ν 3077, 2956, 2927,

1727, 1678, 1597, 1484, 1450, 1353, 1171, 1105, 1084, 1002, 960, 810, 763, 713 cm-1; HRMS (ESI):

calculated for [C20H19NNaO4S]+ 392.09270, found:392.09162.

1-benzoyl-6-methyl-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3g).


16

3gTsN

PhO

OMe

1:4.2 mixture of two isomers, 67% 1H NMR yield. Minor isomer, white solid, 11% isolated yield

(hexanes/ethyl acetate = 1:3): 1H NMR (400 MHz, CDCl3): 7.9δ 1 (d, J = 7.2 Hz, 2H), 7.δ 75 (d, J =

7.2 Hz, 2H), 7.56-7.52 (m, 1H), 7.40-7.31 (m, 4H), 4.12-4.08 (m, 1H), 3.96 (d, J = 10.8 Hz, 1H), 4.12-

4.08 (m, 1H), 2.44 (s, 3H), 2.10-2.03 (m, 1H), 1.22 (d, J = 6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ:

193.1, 167.4, 145.4, 135.7, 134.9, 133.5, 129.7, 129.4, 128.3, 128.2, 44.0, 43.6, 25.5, 25.3, 21.7, 7.0;

Major isomer, white solid, 50% isolated yield (hexanes/ethyl acetate = 1:3): 1H NMR (400 MHz,

CDCl3): 7.9δ 7 (d, J = 7.2 Hz, 2H), 7.δ 86 (d, J = 7.6 Hz, 2H), 7.61-7.57 (m, 1H), 7.48-7.45 (m, 2H),

7.30-7.28 (m, 2H), 4.06 (d, J = 10.4 Hz, 1H), 3.84-3.80 (m, 1H), 2.44 (s, 3H), 2.41 (s, 4H), 1.97-1.94 (m,

1H), 1.04 (d, J = 6.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ: 191.9, 168.7, 145.3, 136.2, 134.6, 134.0,

130.2, 129.7, 128.4, 128.2, 47.0, 43.9, 29.2, 23.5, 21.6, 12.5; MS (EI): m/z (%) = 369 (M+, 1.73), 135

(100)；HRMS (EI): calculated for [C20H19NO4S]+ 369.1035, found: 369.1036.

General Procedure B:



the gold catalyst. 8-methylquinoline N-oxide (63.7 mg, 0.4 mmol) and the premixed catalyst solution

was added sequentially to a solution of enynes 1 (0.2 mmol) in DCE (1 mL) at room temperature under

nitrogen. After stirred at rt for 12 h, the mixture was concentrated and the residue was purified by

column chromatography on silica gel (hexanes/EtOAc = 10:1 to 3:7) to afford the desired product 3.


17

1-benzoyl-3-benzyl-3-azabicyclo[3.1.0]hexan-2-one (3h).

3hBnN

PhO

O


1H NMR (400 MHz, CDCl3): 7.δ 86 (d, J = 7.2 Hz, 2H), 7.58-7.55 (m, 1H), 7.46-7.42 (m, 2H), 7.37-

7.32 (m, 3H),7.27-7.26 (m, 2H), 4.54 (d, J = 14.4 Hz, 1H), 4.26 (d, J = 14.4 Hz, 1H), 3.66-3.62 (m, 1H),

3.30 (d, J = 10.8 Hz, 1H), 2.36-2.35 (m, 1H), 2.03-2.02 (m, 1H), 1.13 (s, 1H); 13C NMR (100 MHz,

CDCl3) δ: 194.7, 171.3, 136.6, 136.4, 133.1, 129.0, 128.8, 128.4, 128.3, 127.9, 47.1, 46.6, 38.6, 22.3,

18.7; IR (neat): ν 3068, 3028, 2926, 2884, 1599, 1580, 1489, 1446, 1423, 1355, 1296, 1269, 1225,

1065, 1026, 1001, 783, 756, 712, 697 cm-1; MS (EI): m/z (%) = 291 (M+, 11.08), 91 (100)； HRMS

(EI): calculated for [C19H17NO2]+ 291.1259, found: 291.1255.

1-pentanoyl-3-tosyl-3-azabicyclo[3.1.0]hexan-2-one (3i).

Yellow oil, 65% yield (hexanes/ethyl acetate = 4:1).

1H NMR (400 MHz, CDCl3) δ: 7.89 (d, J = 7.8 Hz, 2H), 7.35(d, J = 7.8 Hz, 2H), 3.89 (s, 2H), 3.02-

2.94 (m, 1H), 2.79-2.71 (m, 1H), 2.48-2.47 (m, 1H), 2.44 (s, 3H), 1.91-1.89 (m, 1H), 1.51-1.41 (m, 2H),

1.28-1.22 (m, 2H), 1.12 (s, 1H), 0.86 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz) δ: 203.1, 169.4,

145.4, 134.6, 129.8, 128.0, 46.8, 41.5, 38.7, 25.4, 24.0, 23.7, 22.1, 21.7, 13.8. The spectroscopic data

match well with those in the literature.1

1-benzoyl-3-methyl-3-azabicyclo[3.1.0]hexan-2-one (3j).

3i

TsN

BuO

O


18

3jMeN

PhO

O


1H NMR (400 MHz, CDCl3): 7.8δ 7 (d, 2H, J = 7.6 Hz), 7.54-7.52 (m, 1H), 7.46-7.42 (m, 2H), 3.80-

3.76 (m, 1H), 3.39 (d, 1H, J = 10.4 Hz), 2.84 (s, 3H), 2.43-2.41 (m, 1H), 2.01-1.99 (m, 1H), 1.14 (s, 1H).

13C NMR (100 MHz, CDCl3): 194.7, 171.4, 136.5, 133.1, 129.0, 128.3, 49.9,δ 38.5, 29.7, 22.1, 19.3.

The spectroscopic data match well with those in the literature.2

1-(4-methoxybenzoyl)-3-methyl-3-azabicyclo[3.1.0]hexan-2-one (3k).


1H NMR (400 MHz, CDCl3): 7.8δ 8 (d, 2H, J = 8.0 Hz), 6.91 (d, 2H, J = 8.0 Hz), 3.83 (s, 3H), 3.76-

3.72 (m, 1H), 3.37 (d, 1H, J = 10.8 Hz), 2.82 (s, 3H), 2.37-2.36 (m, 1H), 1.92-1.90 (m, 1H), 1.09-1.08

(m, 1H); 13C NMR (100 MHz, CDCl3): 192.6, 171.6, 163.5, 131.5, 129.3, 113.5δ , 55.4, 49.9, 38.3,

29.7, 21.3, 19.0; IR (neat): ν 3086, 3060, 3014, 2964, 2922, 2841, 1676, 1657, 1600, 1576, 1510, 1454,

1428, 1400, 1366, 1315, 1287, 1255, 1175, 1020, 836; MS (EI): m/z (%) = 245 (M+, 6.82), 42 (100)；

HRMS (EI): calculated for [C14H15NO3]+ 245.1052, found:245.1051.

1-benzoylbicyclo[3.1.0]hexan-2-one (3l).



19

1H NMR (400 MHz, CDCl3): 7.δ 78 (d, 2H, J = 7.2 Hz), 7.57 (m, 1H), 7.44 (t, 2H, J = 7.2 Hz), 2.68-

2.63 (m, 1H), 2.50-2.30 (m, 3H), 2.20-2.12 (m, 1H), 2.07-2.06 (m, 1H), 1.48-1.47 (m, 1H); 13C NMR

(100 MHz, CDCl3): δ 209.7, 195.1, 136.3, 133.1, 129.0, 128.3, 45.1, 33.1, 31.7, 21.6, 19.9; IR (neat):

ν 3061, 2947, 2881, 1720, 1666, 1598, 1580, 1449, 1415, 1370, 1318, 1297, 1266, 1208, 1176, 1096,

1066, 1031, 770, 696 cm-1; MS (EI): m/z (%) = 200 (M+, 4.53), 105 (100)；HRMS (EI): calculated for

[C13H12O2]+ 200.0837, found: 200.0838.

1-(4-methoxybenzoyl)bicyclo[3.1.0]hexan-2-one (3m).


1H NMR (400 MHz, CDCl3): 7.δ 79 (d, 2H, J = 8.4 Hz), 6.92 (d, 1H, J = 8.4 Hz), 3.86 (s, 3H), 2.65-

2.60 (m, 1H), 2.45-2.32 (m, 3H), 2.20-2.10 (m, 1H), 2.05-1.95 (m, 1H), 1.48-1.42 (m, 1H); 13C NMR

(100 MHz, CDCl3): δ 209.9, 193.0, 163.6, 131.5, 129.1, 113.6, 55.4, 44.9, 33.1, 30.8, 21.5, 19.7; IR

(neat): ν 3006, 2943, 2841, 1720, 1658, 1597, 1575, 1510, 1458, 1419, 1369, 1309, 1255, 1213, 1166,

1095, 1028, 839, 811, 737 cm-1; MS (EI): m/z (%) = 230 (M+, 22.06), 135 (100)；HRMS (EI):

calculated for [C13H12O2]+ 230.0943, found: 230.0944.

1-(4-methoxybenzoyl)-5-methylbicyclo[3.1.0]hexan-2-one (3n).


1H NMR (400 MHz, CDCl3): 7.δ 63 (d, 2H, J = 8.4 Hz), 6.92 (d, 2H, J = 8.0 Hz), 3.85 (s, 3H), 2.44-

2.18 (m, 4H), 2.07-2.03 (m, 1H), 1.48-1.45 (m, 1H), 1.26 (s, 1H); 13C NMR (100 MHz, CDCl3): δ


20

210.8, 193.2, 163.5, 131.1, 129.9, 113.8, 55.4, 50.7, 40.8, 34.2, 28.9, 23.8, 18.5; IR (neat): ν 3075,

3004, 2954, 2935, 2871, 1721, 1657, 1598, 1574, 1510, 1449, 1419, 1357, 1341, 1310, 1252, 1210,

1167, 1114, 1064, 1026, 843, 823 cm-1; MS (EI): m/z (%) = 244 (M+, 11.84), 135 (100)；HRMS (EI):

calculated for [C15H10O3]+ 244.1099, found: 244.1100.

3-benzyl-1-(4-methoxybenzoyl)bicyclo[3.1.0]hexan-2-one (3o).

3o

O

O

MeO

Bn

Yellow oil, a mixture of diastereomer (1: 1.5), 78% yield (hexanes/ethyl acetate = 10:1).

1H NMR (400 MHz, CDCl3): 7.δ 79 (d, 1.2H, J = 7.2 Hz), 7.69 (d, 0.8H, J = 7.2 Hz), 7.31-7.15 (m,

5H), 6.93 (d, 1.2H, J = 7.6 Hz), 6.89 (d, 0.8H, J = 7.6 Hz), 3.86 (s, 3H), 3.19-2.99 (m, 1.6H), 2.742.45

(m, 3.2H), 2.22-2.14 (m, 0.8H), 1.92-1.85 (m, 1.6H), 1.52-1.51 (m, 0.4H), 1.35 (s, 0.4H), 1.26-1.22 (m,

0.8H), 0.88-0.87 (m, 0.8H); 13C NMR (100 MHz, CDCl3): δ 210.9, 209.6, 193.3, 192.9, 163.58, 163.56,

139.1, 139.0, 131.54, 131.52, 129.3, 129.20, 129.15, 128.5, 126.6, 126.4, 113.63, 113.59, 55.5, 49.7,

46.4, 44.9, 44.4, 38.4, 35.5, 29.3, 29.0, 28.4, 26.9, 21.2, 19.4; IR (neat): ν 3028, 3005, 2934, 2873,

1718, 1658, 1598, 1575, 1510, 1454, 1420, 1310, 1254, 1211, 1165, 1115, 1023, 839, 746, 702 cm-1;

MS (EI): m/z (%) = 320 (M+, 15.51), 135 (100)；HRMS (EI): calculated for [C21H20O3]+ 320.1412,

found: 320.1413.

1-pentanoylbicyclo[3.1.0]hexan-2-one (3p).

3p

BuO

O

Yellow oil, hexanes/ethyl acetate = 10:1, 78% yield.

1H NMR (300 MHz, CDCl3) δ: 3.08-2.97 (m, 1H), 2.85-2.74 (m, 1H), 2.64-2.58 (m, 1H), 2.30-2.24 (m,

2H), 2.20-1.95 (m, 3H), 1.59-1.48 (m, 2H), 1.43-1.40 (m, 1H), 1.35-1.33 (m, 2H), 0.90 (t, J = 9.6 Hz,


21

3H); 13C NMR (CDCl3, 75 MHz) δ: 209.6, 204.7, 45.2, 41.8, 35.6, 34.2, 25.7, 25.2, 20.9, 13.9; IR

(neat): ν 2958, 2935, 2874, 1723, 1689, 1458, 1382, 1304, 1257, 1091, 1034 cm-1; MS (EI): m/z (%) =

180 (M+, 1.77), 55 (100)；HRMS (EI): calculated for [C11H16O2]+ 180.1150, found: 180.1151.

1-benzoyl-3-benzyl-3-azabicyclo[4.1.0]heptan-2-one (3q).


1H NMR (400 MHz, CDCl3): 7.δ 89 (d, J = 7.6 Hz, 2H), 7.56 (t, J = 7.6 Hz, 1H), 7.46 (t, J = 7.6 Hz,

2H), 7.35-7.24 (m, 5H), 4.69 (d, J = 14.4 Hz, 1H), 4.30 (d, J = 14.4 Hz, 1H), 3.27-3.23 (m, 1H), 3.19-

3.12 (m, 1H), 2.31-2.24 (m, 1H), 2.14-2.06 (m, 2H), 2.04 (s, 1H), 1.50 (t, J = 5.6 Hz, 1H); 13C NMR

(100 MHz, CDCl3) δ: 195.6, 168.7, 137.12, 137.06, 132.6, 128.7, 128.3, 128.2, 128.1, 127.6, 50.1,

42.2, 34.6, 24.7, 20.4, 12.2; IR (neat): ν 3086, 3029, 2927, 2863, 1679, 1622, 1496, 1444, 1393, 1324,

1278, 1216, 1186, 1108, 1073, 1002, 740, 695 cm-1; MS (EI): m/z (%) = 305 (M+, 32.29), 91 (100)；

HRMS (EI): calculated for [C20H19NO2]+ 305.1416, found: 305.1417.

2.5 Gold(I)-Catalyzed Reaction of Enyne 1a:



the gold catalyst. The mixture of 2-4 equiv. of pyridine N-oxide and 1a in DCE (1 mL) was treated with

the premixed gold catalyst and stirred at room temperature for 12 h. The mixture was concentrated and


22

the residue was purified by column chromatography on silica gel (hexanes/EtOAc = 3:1) to afford 2a in

30% isolated yield.

1H NMR (400 MHz, CDCl3): δ 8.32 (d, J = 13.2 Hz, 1H), 7.85 (d, J = 7.6 Hz, 2H), 7.76 (d, J = 7.2 Hz, 2H),

7.55-7.51 (m, 1H), 7.46-7.42 (m, 2H), 7.35 (d, J = 8.0 Hz, 2H), 6.23 (d, J = 13.6 Hz, 1H), 5.71-5.63 (m, 1H),

5.26-5.22 (m, 2H), 4.22-4.21 (m, 2H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 189.4, 145.0, 142.5,

138.5, 135.3, 134.2, 134.1, 132.4, 130.2, 129.3, 129.2, 128.5, 128.0, 127.4, 118.7, 103.6, 48.8, 21.6..

2.6 Gold(I)-Catalyzed Reaction of Enyne 1r:

Entry L T (℃) Time (h) Yield (%)a

1 L3 rt 24 53b

2 L4 rt 24 34

3c L4 60 24 51

a 1H NMR yield. b Isolated yield. c 2-bromopydine N-oxide (2.0 eq.).

MeO-DTBM-BIPHEP(AuCl)2 (15.6 mg, 0.010 mmol) was added to a suspension of AgSbF6 (6.8 mg,

0.020 mmol) in DCM (1 mL) at room temperature under nitrogen for 30 min to generate the gold

catalyst. 2-bromopydine N-oxide (41.8 mg, 0.24 mmol), MsOH (0.12 mmol) and the premixed catalyst

solution was added sequentially to a solution of enynes 1r (0.2 mmol) in DCE (1 mL) at room

temperature under nitrogen. After stirred for 24 h, the reaction was treated with saturated aqueous

NaHCO3 (5 mL), and the resulting solution was extracted with DCM (3 × 5 mL). The combined

organic layers were dried with anhydrous Na2SO4. The mixture was concentrated and the residue was


23

purified by column chromatography on silica gel (hexanes/EtOAc = 5:1) to afford 5 in 53% isolated

yield.

1H NMR (400 MHz, CDCl3): δ 8.02 (d, J = 7.6 Hz, 2H), 7.67-7.65 (m, 1H), 7.53-7.50 (m, 2H), 6.26 (s, 1H),

5.87-5.77 (m, 1H), 5.29-5.22 (m, 2H), 4.72-4.71 (m, 2H), 3.25 (s, 3H); 13C NMR (100 MHz, CDCl3): δ

187.9, 164.3, 134.7, 134.4, 130.4, 129.4, 129.0, 119.6, 67.2, 39.7.

2.7 Crystal Structure of Bicyclo [3.1.0]hexan-2one 3f:


24

3. References:

1. X. Tong,M. Beller and M. K. Tse, J. Am. Chem. Soc. 2007, 129, 4906.

2. L. L. Welbes, T. W. Lyons, K. A. Cychosz and M. S. Sanford, J. Am. Chem. Soc. 2007, 129, 5836.

3. H. Peng and G. Liu, Org. Lett., 2011, 13, 772.

4. T. L.Young, K. C. Young and K. K. Youn, J. Org. Chem. 2009, 74, 7922.

5. H. Jiang, S. Ma, G. Zhu and X. Lu, Tetrahedron 1996, 52, 10945.

6. X. Xie, X. Lu and Y. Liu, J. Org. Chem. 2001, 66, 6545.

7. M. Schelwies, R. Moser, A. L. Dempwolff, F. Rominger and G. Helmchen, Chem. Eur. J. 2009, 15,

10888.

8. P. Kraft, and A. Bruneau, Eur. J. Org. Chem. 2007, 2257.


25

9. D. H. Kim and S. Chung, Tetrahedron: Asymmetry 1999, 10, 3769.

10. W. E. Brenzovich, D. Jr. Benitez , A. D. Lackner, H. P. Shunatona, E. Tkatchouk, W.

A., III Goddard, and F. D. Toste, Angew. Chem., Int. Ed. 2010, 49, 5519

11. T. Kobayashi, Y. Koga and K. Narasaka, J. Organomet. Chem. 2001, 624, 73.

12. V. Mamane, T. Gress, H. Krause, A. Fürstner, J. Am. Chem. Soc. 2004, 126, 8654

13. H. Kuroda, E. Hanakia, H. Izawaa, M. Kanoa and H. Itahashia, Tetrahedron 2004, 60, 1913.

14. C. Taillier, T. Hameury, V. Bellosta and J. Cossy Tetrahedron 2007, 63, 4472.

4. 1H and 13C NMR Spectra for New Compounds


9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.600

2.419

3.836

4.672

4.685

5.287

5.312

5.374

5.417

5.924

5.938

5.950

5.964

5.978

5.992

6.003

6.017

6.875

6.894

7.260

7.285

7.304

7.465

7.484

7.899

7.918

3.12

3.10

2.06

2.05

1.00

2.06

2.03

2.04

2.02

qdy−3−137−3 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

21.60

49.35

55.41

76.69

77.00

77.32

81.18

93.97

111.11

114.42

118.78

128.67

129.37

132.55

134.69

136.01

144.98

152.76

161.82

qdy−2−137 CElectronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

2.396

4.771

5.324

5.349

5.421

5.463

6.004

6.022

6.037

7.264

7.283

7.438

7.455

7.472

7.545

7.566

7.588

7.767

7.784

7.858

7.877

7.935

7.951

8.237

8.256

3.18

2.03

2.07

1.00

2.17

1.06

2.10

1.02

1.10

3.08

0.99

qdy−3−95 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

21.61

49.38

76.68

77.00

77.32

85.95

91.77

116.96

118.93

125.07

125.66

127.00

127.76

128.51

128.71

129.45

131.68

132.45

132.93

132.97

133.49

135.93

145.11

152.63

qdy−3−95 C


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

1.663

1.724

1.739

1.799

1.816

2.418

4.616

4.630

4.743

4.758

5.553

5.602

5.624

5.640

5.715

5.736

5.754

5.843

5.860

5.879

5.896

7.268

7.285

7.304

7.365

7.381

7.399

7.447

7.463

7.481

7.511

7.530

7.889

7.906

2.44

0.50

3.00

1.63

0.33

0.20

0.78

0.18

0.80

2.12

1.99

1.07

1.82

1.95

qdy−3−48−2 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

13.11

17.62

21.56

44.20

48.92

76.68

77.00

77.32

81.64

92.81

119.46

125.01

125.29

128.54

128.64

129.31

129.37

130.88

131.04

132.61

136.13

144.91

152.54

qdy−3−48−2 CElectronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

2.968

3.213

3.820

4.059

4.073

4.234

4.247

5.181

5.201

5.227

5.270

5.713

5.728

5.744

5.754

5.769

5.801

5.813

5.828

5.845

5.856

5.867

6.857

6.878

7.260

7.458

7.480

7.502

1.76

1.24

3.04

0.84

1.18

2.00

0.98

2.02

2.00

qdy−3−17 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

31.95

35.77

48.89

53.68

55.33

76.68

77.00

77.32

80.72

80.90

90.32

90.88

112.43

114.17

117.83

117.96

132.06

132.65

134.12

154.70

154.91

160.97

qdy−3−17 C


Administrator

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.454

2.470

2.487

2.504

2.728

2.746

2.765

3.833

5.007

5.033

5.064

5.107

5.799

5.816

5.825

5.840

5.858

5.868

5.876

5.898

6.877

6.896

7.260

7.509

7.530

2.05

2.01

3.55

2.05

1.00

2.44

2.18

qdy−3−142 HElectronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

28.10

44.36

55.37

76.68

77.00

77.31

87.64

92.08

111.67

114.33

114.47

115.60

135.06

135.39

136.41

161.63

187.11


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

−0.006

1.614

1.768

2.422

2.440

2.459

2.779

2.798

2.816

3.841

4.728

4.772

6.885

6.906

7.260

7.519

7.540

2.96

2.00

2.00

3.07

1.99

2.03

2.01

qdy−4−5 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

22.63

31.83

43.52

55.40

76.68

77.00

77.32

87.64

92.07

110.60

111.71

114.34

135.09

143.83

161.62

187.44

qdy−4−5 C


Administrator

图章

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.609

2.362

2.381

2.398

2.431

2.501

2.519

2.537

2.555

2.573

2.826

2.842

2.860

2.876

2.988

3.005

3.022

3.038

3.054

3.110

3.128

3.144

3.162

3.839

5.062

5.086

5.127

5.736

5.755

5.765

5.777

5.797

5.818

5.837

6.885

6.906

7.176

7.199

7.259

7.278

7.296

7.502

7.523

1.10

1.04

1.02

1.18

1.04

3.21

2.02

1.00

2.15

3.07

2.40

2.14


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

35.09

36.74

55.40

55.58

76.68

77.00

77.32

87.29

93.27

111.71

114.34

117.49

126.36

128.32

128.42

128.51

129.06

134.76

135.10

138.89

161.67

190.07


Administrator

图章

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.898

0.915

0.934

1.396

1.414

1.432

1.450

1.519

1.536

1.553

1.571

1.589

1.650

2.340

2.358

2.376

2.388

2.405

2.422

2.605

2.623

2.641

4.978

5.003

5.019

5.063

5.748

5.766

5.775

5.789

5.807

5.827

5.848

7.260

3.32

2.17

2.21

4.17

1.99

2.05

1.00

qdy−3−133−H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

13.43

18.59

21.91

27.97

29.67

44.48

76.68

77.00

77.32

80.74

94.62

115.51

136.40

187.37

qdy−3−133−C


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.281

2.298

2.316

2.333

2.366

2.384

2.401

2.418

3.417

3.435

3.453

3.613

3.631

3.649

4.692

4.873

5.026

5.049

5.072

5.094

5.114

5.732

5.741

5.755

5.774

5.781

5.799

5.822

7.262

7.285

7.301

7.330

7.355

7.373

7.391

7.409

7.424

7.476

7.495

7.536

7.554

1.05

1.01

1.04

1.00

1.01

1.05

2.03

1.00

8.05

1.07

1.03


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

31.53

32.99

43.75

47.60

47.76

52.94

76.68

77.00

77.32

81.69

81.83

90.10

90.30

116.97

117.51

120.40

120.51

127.47

127.58

127.88

128.13

128.44

128.52

128.65

128.81

130.00

130.04

132.35

132.38

134.31

134.93

136.44

136.59

154.72

154.91

qdy−3−143 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.359

1.967

1.982

1.995

2.456

2.534

2.547

4.020

4.046

4.066

4.093

7.260

7.328

7.341

7.516

7.535

7.553

7.694

7.712

7.893

7.911

1.09

1.00

3.03

1.03

2.04

4.03

1.04

1.97

1.98

qdy−2−128−1 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.20

21.41

21.67

38.60

47.30

76.69

77.00

77.32

128.15

128.34

129.23

129.77

133.56

134.50

135.48

145.43

169.25

192.18

qdy−2−128−1 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.333

1.945

2.374

2.451

2.507

4.049

4.076

7.112

7.130

7.260

7.320

7.338

7.588

7.606

7.888

7.906

1.08

1.00

2.99

3.01

1.13

1.96

2.03

2.03

1.98

1.99

qdy−3−72 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.01

21.15

21.63

21.69

38.51

47.28

76.68

77.00

77.32

128.10

129.03

129.33

129.72

132.86

134.39

144.54

145.35

169.39

191.58

qdy−3−72 H


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

−0.001

1.342

1.353

1.881

1.896

1.910

2.453

2.502

2.515

2.530

3.855

3.987

4.012

4.025

4.053

4.079

6.822

6.841

7.260

7.327

7.346

7.739

7.758

7.898

7.916

1.13

1.05

3.03

1.10

3.01

2.08

2.00

2.02

1.97

1.96

qdy−2−1440−1 HElectronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.16

20.56

21.66

38.43

47.30

55.47

76.68

77.00

77.32

113.65

128.15

128.29

129.76

131.83

134.48

145.40

163.98

169.53

190.12

qdy−2−140 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.399

2.216

2.421

2.695

4.073

7.247

7.265

7.289

7.308

7.326

7.454

7.466

7.582

7.599

7.794

7.814

7.933

7.953

8.255

8.270

1.07

1.08

3.21

1.00

2.07

3.31

2.09

1.13

3.16

1.15

1.01

qdy−3−99 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

21.05

21.70

24.08

40.06

47.07

76.76

77.08

77.40

124.09

124.95

126.47

127.88

128.04

128.55

128.60

129.75

130.21

133.01

133.78

133.84

134.50

145.34

168.83

195.50

qdy−3−99 H


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.244

2.079

2.483

3.904

3.930

4.146

4.172

7.230

7.248

7.265

7.351

7.370

7.408

7.426

7.475

7.492

7.509

7.912

7.930

4.22

1.14

3.04

1.02

1.00

2.12

2.06

1.90

1.02

1.98

qdy−3−42−2 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

15.71

21.76

22.65

31.43

43.38

52.92

76.78

77.10

77.42

128.19

128.46

128.57

129.84

133.33

134.61

136.44

145.49

170.51

191.80

qdy−3−42−2 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.217

1.232

1.256

1.632

2.032

2.048

2.065

2.082

2.098

2.440

2.595

2.612

2.630

3.949

3.976

4.079

4.095

4.121

7.262

7.312

7.332

7.359

7.377

7.396

7.524

7.542

7.561

7.742

7.761

7.901

7.919

3.23

0.99

3.26

0.97

1.00

1.00

4.15

1.08

1.92

2.02

qdy−3−136−H min


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

6.95

21.66

25.31

25.54

43.56

43.95

76.68

77.00

77.31

128.21

128.30

129.38

129.73

133.47

134.90

135.71

145.43

167.44

193.12

qdy−3−136−C min


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.035

1.050

1.635

1.941

1.955

1.969

2.411

3.799

3.821

3.837

4.049

4.075

7.262

7.279

7.298

7.445

7.464

7.482

7.570

7.588

7.606

7.855

7.874

7.961

7.979

2.89

0.95

4.12

0.98

1.00

2.31

1.95

1.01

1.85

1.92

qdy−3−136−H maj


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

12.53

21.62

23.46

29.16

43.90

46.96

76.68

77.00

77.32

128.13

128.41

129.74

130.20

133.95

134.59

136.17

145.30

168.71

191.90

qdy−3−136 C majElectronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2011

Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.131

2.019

2.029

2.348

2.362

3.282

3.308

3.621

3.635

3.644

3.660

4.243

4.279

4.529

4.565

7.255

7.269

7.323

7.351

7.368

7.423

7.441

7.459

7.547

7.566

7.583

7.846

7.864

1.00

1.01

0.96

0.97

0.98

0.98

0.97

2.28

3.12

2.01

1.00

1.87

qdy−3−8−1 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

18.71

22.29

38.57

46.57

47.14

76.68

77.00

77.32

127.85

128.26

128.38

128.79

129.04

133.10

136.41

136.59

171.32

194.65

qdy−3−8−1 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.260

1.277

1.407

1.424

1.441

1.458

1.476

1.493

1.509

1.888

1.897

1.907

2.439

2.471

2.476

2.710

2.728

2.751

2.772

2.786

2.942

2.960

2.981

3.004

3.019

3.891

7.260

7.337

7.356

7.877

7.896

3.14

1.03

2.20

2.07

1.00

4.16

1.00

1.00

2.02

2.11

2.02

qdy−3−97−1 H

0.81.01.2 ppm

0.824

0.842

0.858

1.118

1.224

1.242

1.260

1.277


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

13.80

21.66

22.08

23.68

24.03

25.43

38.73

41.49

46.77

76.68

77.00

77.32

127.98

129.75

134.62

145.44

169.36

203.05

qdy−3−97−1 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.136

1.994

2.002

2.012

2.414

2.428

2.836

3.376

3.402

3.761

3.775

3.785

3.801

7.260

7.423

7.441

7.458

7.527

7.544

7.561

7.863

7.882

1.03

1.15

1.00

3.01

1.00

1.01

1.98

1.05

2.00

qdy−3−86 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.28

22.13

29.71

38.53

49.92

76.68

77.00

77.32

128.25

129.03

133.06

136.54

171.43

194.73


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.081

1.089

1.904

1.912

1.922

2.363

2.371

2.818

3.345

3.372

3.722

3.733

3.744

3.759

3.833

6.899

6.919

7.260

7.871

7.891

1.04

1.30

1.02

3.03

1.01

1.04

3.06

2.02

2.00

qdy−3−85 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.02

21.30

29.65

38.28

49.89

55.37

76.69

77.00

77.32

113.48

129.34

131.51

163.50

171.61

192.63

qdy−3−85 C


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

0.069

1.472

1.480

1.679

2.061

2.070

2.151

2.168

2.178

2.187

2.342

2.371

2.417

2.427

2.442

2.651

2.661

7.260

7.425

7.442

7.461

7.534

7.552

7.569

7.769

7.788

1.01

1.03

1.00

3.05

1.00

2.02

1.01

1.97

qdy−3−128 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.85

21.57

31.74

33.14

45.06

76.68

77.00

77.32

128.33

129.03

133.10

136.26

195.06

209.69

qdy−3−128 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.441

1.453

1.465

1.972

1.987

2.002

2.134

2.151

2.171

2.335

2.363

2.401

2.420

2.619

2.629

3.857

6.913

6.934

7.260

7.781

7.802

1.02

1.04

1.00

3.07

1.00

2.03

1.99

qdy−3−145 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.74

21.49

30.83

33.10

44.88

55.41

76.68

77.00

77.32

113.58

129.09

131.50

163.56

193.03

209.94

qdy−3−145 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.258

1.457

1.468

2.058

2.064

2.199

2.230

2.257

2.284

2.309

2.343

2.365

2.395

2.441

3.849

6.913

6.933

7.260

7.623

7.644

3.27

1.00

1.02

4.11

3.18

2.09

1.93

qdy−4−27 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

18.51

23.85

28.92

34.17

40.83

50.72

55.44

76.68

77.00

77.32

113.78

129.89

131.11

163.47

193.18

210.76

qdy−4−15 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.224

1.255

1.345

1.509

1.519

1.854

1.891

1.916

2.135

2.144

2.212

2.221

2.449

2.533

2.576

2.603

2.626

2.681

2.708

2.736

2.993

3.014

3.057

3.092

3.167

3.189

3.864

6.877

6.896

6.922

6.941

7.145

7.164

7.193

7.238

7.253

7.291

7.305

7.686

7.704

7.783

7.801

0.77

0.82

0.40

0.45

1.62

0.89

3.14

1.63

3.00

0.83

1.15

5.31

0.83

1.14

qdy−4−8 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

19.38

21.15

26.84

28.35

28.97

29.27

35.51

38.37

44.38

44.88

46.45

49.73

55.44

76.68

77.00

77.32

126.36

126.62

128.50

128.61

129.03

129.20

131.51

138.99

139.14

163.55

192.85

193.25

209.61

210.93

qdy−4−8 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

0.872

0.896

0.920

1.239

1.280

1.305

1.330

1.354

1.397

1.412

1.415

1.430

1.475

1.498

1.523

1.538

1.544

1.562

1.672

1.992

1.998

2.009

2.023

2.031

2.055

2.069

2.082

2.096

2.116

2.132

2.148

2.164

2.189

2.244

2.255

2.270

2.284

2.303

2.579

2.597

2.604

2.615

2.623

2.741

2.764

2.767

2.790

2.799

2.821

2.826

2.848

2.970

2.991

2.997

3.019

3.027

3.050

3.054

7.260

3.07

2.25

1.03

2.05

1.08

1.17

1.01

1.91

0.99

1.02

1.00

qdy−3−146 H

2.62.72.82.93.03.13.2 ppm

2.579

2.597

2.604

2.615

2.623

2.641

2.741

2.764

2.767

2.790

2.799

2.821

2.826

2.848

2.970

2.991

2.997

3.019

3.027

3.050

3.054

3.077

2.02.12.22.3 ppm

1.992

1.998

2.009

2.023

2.031

2.055

2.069

2.082

2.096

2.116

2.132

2.148

2.164

2.189

2.203

2.244

2.255

2.270

2.284

2.303

1.21.31.41.51.61.7 ppm

1.239

1.255

1.280

1.305

1.330

1.354

1.378

1.397

1.412

1.415

1.430

1.452

1.475

1.488

1.498

1.523

1.538

1.544

1.562

1.588

1.672


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

13.90

20.89

22.26

25.16

25.69

34.22

35.57

41.81

45.17

76.58

77.00

77.43

204.71

209.60

qdy−3−146 C


Administrator

图章

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.469

1.482

1.496

1.854

2.043

2.060

2.077

2.104

2.136

2.239

2.255

2.277

2.284

2.312

3.123

3.147

3.155

3.179

3.186

3.226

3.241

3.258

3.274

4.394

4.430

4.653

4.689

7.235

7.253

7.290

7.315

7.333

7.351

7.424

7.442

7.461

7.519

7.537

7.556

7.872

7.891

1.00

1.00

2.00

1.00

0.99

0.97

0.98

0.98

5.07

1.97

1.01

1.93

qdy−4−7 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

12.18

20.38

24.68

34.57

42.23

50.13

76.68

77.00

77.32

127.58

128.14

128.24

128.30

128.65

132.57

137.06

137.12

168.72

195.61

qdy−4−7 C


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

−0.004

1.636

2.434

4.208

4.220

5.216

5.230

5.257

5.614

5.626

5.639

5.654

5.668

5.682

5.694

5.707

6.192

6.226

7.260

7.327

7.347

7.423

7.442

7.460

7.511

7.529

7.547

7.738

7.756

7.831

7.850

8.286

8.319

3.00

1.92

0.89

1.02

0.94

0.96

1.96

2.15

1.38

1.92

1.92

0.93

qdy−2−50−2 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

21.61

48.76

76.68

77.00

77.32

103.63

118.74

127.35

127.99

128.48

129.16

129.27

130.17

130.28

132.36

134.06

134.19

135.33

138.52

142.49

144.99

189.35

qdy−2−50−2 H


Administrator

图章

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm

3.249

4.707

4.718

4.721

5.216

5.242

5.285

5.772

5.786

5.800

5.813

5.829

5.843

5.855

5.869

6.260

7.260

7.497

7.516

7.534

7.631

7.633

7.650

7.668

8.001

8.020

3.15

2.08

2.02

1.00

1.00

2.20

1.08

2.09

qdy−3−40−2 H


Administrator

图章

200 180 160 140 120 100 80 60 40 20 0 ppm

39.67

67.20

76.69

77.00

77.32

119.63

128.96

129.39

130.42

133.44

134.67

164.34

187.88

qdy−3−40−2 C


Administrator

图章

Date post:	22-Sep-2020
Category:	Documents
Upload:	others
View:	0 times
Download:	0 times

Gold(I)-Catalyzed Intramolecular Oxidation ... · 5 2.2 The Control Experiments Regarding Acid...

Documents