Supporting Information Construction of the biaryl-part of … · 2012. 4. 3. · SI#1% % Supporting...

SI-‐1

Supporting Information

Construction of the biaryl-part of Vancomycin Aglycon via atropo-diastereoselective Suzuki-Miyaura coupling

Timo Leermann,a Pierre-Emmanuel Broutin,a Frédéric R. Leroux,*a and Françoise Colobert*a

Contents:

NMR spectra SI-2

Crystallographic data SI-8

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

SI-‐2

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 0Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

9.292.990.920.771.761.81


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

Nor

mal

ized

Inte

nsity

9.343.180.770.821.031.041.00

OMe

NHBocMeO2C

11

OMe

NHBocMeO2C

12

I


SI-‐3


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

Nor

mal

ized

Inte

nsity

12.843.110.910.741.081.061.01

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 0Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

3.300.991.00

OMe

NHBocMeO2C

6

BO

O

OMe

MeO CO2Me

I

14


SI-‐4


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

3.023.032.170.952.052.07


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

3.012.183.050.970.970.961.931.92

OMe

MeO

I O

Sp-Tol

O:

15

OMe

MeO

I OH

Sp-Tol

O:

16


SI-‐5


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

2.963.062.143.021.021.022.082.06


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Nor

mal

ized

Inte

nsity

2.945.026.150.980.910.961.931.85

OMe

MeO

I OAc

Sp-Tol

O:

7

OMe

MeO

I OMe

Sp-Tol

O:

8


SI-‐6


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

9.413.263.392.393.213.250.951.170.911.161.201.162.17


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

Nor

mal

ized

Inte

nsity

9.482.973.221.161.236.133.021.080.961.181.081.121.165.44

MeO2C NHBoc

OMe

MeO OMe

OAcSp-Tol

O:

(aS)-4: Rotamer I

MeO2C NHBoc

OMe

MeO OMe

OAcSp-Tol

O:

(aS)-4: Rotamer II


SI-‐7


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Norm

alize

d In

tens

ity

9.143.343.282.293.031.181.011.041.292.301.291.10


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Nor

mal

ized

Inte

nsity

8.733.003.062.711.051.121.041.171.251.034.07

MeO2C NHBoc

OMe

MeO OMe

OMeSp-Tol

O:

(aS)-5

MeO2C NHBoc

MeO

MeO

OMe

OMe

SO

p-Tol:

(aR)-5


SI-‐8

Crystallographic data

aS-4:

Crystal data

C36H20N4O6S F(000) = 1312

Mr = 636.62 Dx = 1.219 Mg m−3

a = 9.5048 (3) Å Mo Kα radiation, λ = 0.71073 Å

b = 18.9754 (6) Å µ = 0.14 mm−1

c = 19.2401 (7) Å T = 296 K

α = 90° V = 3470.1 (2) Å3

β = 90° Z = 4

γ = 90°

Data collection

Radiation source: fine-focus sealed tube Rint = 0.041

graphite θmax = 27.5°, θmin = 1.5°

15051 measured reflections h = −9 12


SI-‐9

5726 independent reflections k = −18 17

5091 reflections with I > 2σ(I) l = −21 22

Refinement

wR(F2) = 0.207 Δρmax = 0.50 e Å−3

S = 1.39 Δρmin = −0.38 e Å−3

5726 reflections 415 parameters

Flack parameter: 0.18 (14)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

S1 0.16659 (10) 0.68888 (7) 0.21009 (6) 0.0314 (3)

O1 0.2384 (4) 0.7568 (2) 0.1921 (2) 0.0461 (10)

C1 0.2791 (4) 0.6190 (3) 0.1814 (2) 0.0278 (11)

C5 0.4769 (5) 0.5830 (3) 0.1134 (3) 0.0384 (13)

C4 0.4472 (5) 0.5120 (3) 0.1271 (3) 0.0382 (13)

C6 0.3923 (5) 0.6369 (3) 0.1402 (3) 0.0335 (12)

C2 0.2457 (4) 0.5480 (3) 0.1951 (3) 0.0398 (13)

C3 0.3273 (5) 0.4952 (3) 0.1688 (3) 0.0439 (14)

C7 0.5406 (6) 0.4541 (3) 0.0974 (4) 0.0579 (18)

C8 0.1073 (4) 0.7296 (3) 0.3429 (2) 0.0263 (10)

O10 0.3284 (5) 0.7728 (3) 0.4174 (3) 0.0783 (16)

C11 0.2355 (5) 0.7429 (3) 0.4493 (3) 0.0462 (16)

C9 0.1923 (4) 0.6750 (3) 0.3023 (2) 0.0280 (11)

C12 0.2277 (8) 0.7310 (4) 0.5248 (4) 0.070 (2)

O2 0.1219 (3) 0.71540 (19) 0.41637 (18) 0.0347 (9)

C17 −0.1179 (4) 0.6610 (3) 0.3370 (2) 0.0278 (11)

C15 −0.3331 (4) 0.7124 (2) 0.2934 (3) 0.0271 (11)

C13 −0.0491 (4) 0.7255 (2) 0.3267 (2) 0.0225 (10)

C16 −0.2598 (4) 0.6558 (3) 0.3213 (2) 0.0268 (11)

C14 −0.1205 (4) 0.7842 (2) 0.3011 (2) 0.0239 (10)


SI-‐10

O3 −0.3165 (3) 0.59092 (18) 0.33431 (19) 0.0350 (9)

O4 −0.3276 (3) 0.83538 (18) 0.2584 (2) 0.0409 (9)

C18 −0.4746 (5) 0.8297 (3) 0.2390 (4) 0.063 (2)

C19 −0.0465 (3) 0.8526 (2) 0.2893 (3) 0.0259 (10)

C24 0.0686 (4) 0.9324 (2) 0.2090 (3) 0.0277 (11)

C25 −0.0154 (4) 0.8736 (2) 0.2220 (2) 0.0256 (10)

C23 0.1174 (4) 0.9727 (3) 0.2646 (3) 0.0316 (12)

C22 0.0833 (4) 0.9538 (3) 0.3311 (3) 0.0325 (12)

C20 0.0040 (4) 0.8941 (3) 0.3445 (3) 0.0284 (11)

C21 0.0415 (7) 0.9043 (4) 0.4678 (3) 0.0577 (18)

O5 −0.0278 (3) 0.8696 (2) 0.40933 (17) 0.0359 (9)

C27 −0.0175 (4) 0.9532 (3) 0.0891 (3) 0.0303 (11)

C26 0.1137 (4) 0.9480 (3) 0.1339 (3) 0.0308 (11)

C28 −0.2060 (5) 1.0273 (3) 0.0567 (4) 0.0530 (17)

O6 −0.0744 (3) 1.0172 (2) 0.0948 (2) 0.0410 (9)

O7 −0.0659 (4) 0.9074 (2) 0.0544 (2) 0.0507 (11)

N1 0.2046 (4) 0.8904 (2) 0.1116 (2) 0.0366 (11)

O9 0.3486 (4) 0.83660 (19) 0.0397 (2) 0.0428 (10)

O8 0.2742 (4) 0.9494 (2) 0.0141 (2) 0.0530 (12)

C29 0.2755 (5) 0.8969 (3) 0.0512 (3) 0.0370 (13)

C33 0.5586 (7) 0.8842 (4) −0.0177 (4) 0.067 (2)

C34 0.3500 (7) 0.8376 (5) −0.0890 (4) 0.075 (2)

C31 0.4395 (5) 0.8296 (3) −0.0219 (3) 0.0491 (16)

C32 0.4979 (8) 0.7553 (4) −0.0127 (5) 0.079 (3)

C36 −0.2632 (4) 0.7760 (3) 0.2843 (3) 0.0262 (11)

C37 −0.4604 (4) 0.5797 (3) 0.3200 (3) 0.0463 (15)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23


SI-‐11

S1 0.0254 (4) 0.0396 (9) 0.0291 (6) 0.0055 (4) −0.0032 (4) 0.0019 (6)

O1 0.0531 (19) 0.039 (3) 0.046 (2) 0.0089 (17) 0.0069 (16) 0.007 (2)

C1 0.0234 (15) 0.030 (3) 0.030 (3) 0.0009 (16) −0.0077 (16) −0.004 (2)

C5 0.034 (2) 0.045 (4) 0.036 (3) −0.002 (2) 0.0038 (19) −0.006 (3)

C4 0.036 (2) 0.042 (4) 0.036 (3) −0.002 (2) −0.0055 (19) −0.001 (3)

C6 0.039 (2) 0.034 (3) 0.028 (3) −0.004 (2) 0.0026 (18) 0.000 (2)

C2 0.0277 (18) 0.043 (4) 0.048 (3) −0.0095 (19) 0.0017 (18) 0.001 (3)

C3 0.037 (2) 0.037 (4) 0.058 (4) −0.001 (2) −0.004 (2) 0.000 (3)

C7 0.047 (3) 0.047 (4) 0.080 (5) 0.014 (3) 0.001 (3) −0.023 (4)

C8 0.0221 (16) 0.035 (3) 0.021 (2) 0.0024 (16) −0.0040 (14) 0.002 (2)

O10 0.060 (2) 0.103 (4) 0.072 (3) −0.030 (3) −0.023 (2) −0.009 (3)

C11 0.039 (2) 0.045 (4) 0.055 (4) 0.004 (2) −0.019 (2) −0.023 (3)

C9 0.0224 (15) 0.034 (3) 0.027 (3) 0.0050 (15) −0.0028 (14) −0.003 (2)

C12 0.085 (4) 0.085 (6) 0.041 (4) 0.022 (4) −0.031 (3) −0.016 (4)

O2 0.0313 (13) 0.042 (2) 0.031 (2) 0.0004 (13) −0.0093 (13) −0.0054 (16)

C17 0.0216 (15) 0.031 (3) 0.031 (3) 0.0020 (16) 0.0011 (15) −0.003 (2)

C15 0.0195 (14) 0.022 (3) 0.040 (3) 0.0017 (14) −0.0039 (17) 0.004 (2)

C13 0.0197 (15) 0.021 (3) 0.027 (2) −0.0011 (14) 0.0003 (14) −0.002 (2)

C16 0.0222 (16) 0.028 (3) 0.030 (2) −0.0023 (15) 0.0020 (15) −0.003 (2)

C14 0.0235 (15) 0.021 (3) 0.027 (3) −0.0038 (14) 0.0018 (15) −0.003 (2)

O3 0.0245 (13) 0.025 (2) 0.055 (2) −0.0051 (12) −0.0009 (13) 0.0061 (17)

O4 0.0243 (13) 0.030 (2) 0.069 (3) 0.0012 (13) −0.0130 (15) 0.0089 (19)

C18 0.026 (2) 0.051 (4) 0.112 (6) 0.001 (2) −0.028 (3) 0.012 (4)

C19 0.0206 (14) 0.024 (3) 0.033 (3) 0.0014 (14) −0.0010 (16) −0.002 (2)

C24 0.0239 (15) 0.027 (3) 0.032 (3) 0.0019 (15) 0.0046 (16) −0.003 (2)

C25 0.0250 (16) 0.017 (3) 0.035 (3) 0.0039 (15) −0.0013 (16) 0.000 (2)

C23 0.0293 (18) 0.026 (3) 0.039 (3) 0.0038 (17) 0.0037 (17) −0.006 (2)

C22 0.0314 (18) 0.021 (3) 0.045 (3) −0.0002 (17) −0.0012 (19) −0.004 (2)

C20 0.0253 (16) 0.025 (3) 0.035 (3) 0.0020 (16) 0.0022 (16) 0.002 (2)


SI-‐12

C21 0.074 (4) 0.063 (5) 0.037 (3) −0.021 (3) 0.003 (3) −0.024 (3)

O5 0.0442 (16) 0.038 (2) 0.0254 (19) −0.0105 (15) 0.0025 (13) −0.0078 (17)

C27 0.038 (2) 0.022 (3) 0.031 (3) −0.0005 (19) 0.0046 (18) 0.003 (2)

C26 0.0264 (17) 0.028 (3) 0.038 (3) 0.0020 (16) 0.0069 (17) −0.002 (2)

C28 0.041 (2) 0.046 (4) 0.072 (4) 0.015 (2) −0.021 (3) −0.007 (3)

O6 0.0403 (16) 0.032 (3) 0.051 (2) 0.0045 (15) −0.0094 (15) −0.0078 (19)

O7 0.065 (2) 0.036 (3) 0.052 (3) 0.0014 (19) −0.0176 (19) −0.014 (2)

N1 0.0359 (18) 0.033 (3) 0.041 (3) 0.0048 (16) 0.0137 (16) 0.000 (2)

O9 0.0461 (17) 0.030 (2) 0.053 (2) 0.0034 (15) 0.0243 (16) −0.0014 (19)

O8 0.062 (2) 0.038 (3) 0.059 (3) 0.0145 (19) 0.032 (2) 0.015 (2)

C29 0.0311 (19) 0.031 (4) 0.049 (3) 0.0019 (18) 0.017 (2) 0.006 (3)

C33 0.057 (3) 0.055 (5) 0.089 (5) −0.005 (3) 0.037 (3) −0.005 (4)

C34 0.062 (4) 0.104 (7) 0.058 (5) 0.007 (4) 0.022 (3) −0.017 (4)

C31 0.043 (2) 0.048 (4) 0.056 (4) 0.007 (2) 0.022 (2) −0.008 (3)

C32 0.105 (6) 0.023 (4) 0.109 (6) 0.025 (4) 0.065 (5) 0.006 (4)

C36 0.0237 (16) 0.020 (3) 0.035 (3) 0.0039 (15) −0.0036 (16) 0.003 (2)

C37 0.0244 (17) 0.040 (4) 0.074 (4) −0.0111 (19) −0.012 (2) 0.012 (3)

Geometric parameters (Å, °)

S1—O1 1.499 (4) O3—C37 1.411 (5)

S1—C1 1.791 (5) O4—C36 1.376 (5)

S1—C9 1.810 (5) O4—C18 1.450 (5)

C1—C6 1.379 (6) C19—C25 1.387 (7)

C1—C2 1.408 (7) C19—C20 1.406 (7)

C5—C6 1.400 (7) C24—C23 1.394 (7)

C5—C4 1.401 (8) C24—C25 1.395 (6)

C4—C3 1.430 (7) C24—C26 1.535 (7)

C4—C7 1.525 (7) C23—C22 1.369 (7)

C2—C3 1.364 (7) C22—C20 1.385 (6)


SI-‐13

C8—O2 1.446 (6) C20—O5 1.364 (6)

C8—C13 1.522 (5) C21—O5 1.460 (7)

C8—C9 1.529 (6) C27—O7 1.189 (6)

O10—C11 1.217 (8) C27—O6 1.334 (6)

C11—O2 1.356 (5) C27—C26 1.519 (6)

C11—C12 1.472 (9) C26—N1 1.458 (6)

C17—C16 1.385 (5) C28—O6 1.463 (6)

C17—C13 1.402 (6) N1—C29 1.349 (6)

C15—C16 1.387 (6) O9—C29 1.357 (6)

C15—C36 1.389 (6) O9—C31 1.472 (6)

C13—C14 1.394 (6) O8—C29 1.224 (6)

C16—O3 1.368 (6) C33—C31 1.536 (8)

C14—C36 1.403 (5) C34—C31 1.553 (10)

C14—C19 1.494 (6) C31—C32 1.525 (9)

O1—S1—C1 107.1 (2) C25—C19—C20 118.2 (4)

O1—S1—C9 106.8 (2) C25—C19—C14 119.4 (4)

C1—S1—C9 96.5 (2) C20—C19—C14 122.2 (4)

C6—C1—C2 121.3 (5) C23—C24—C25 119.4 (5)

C6—C1—S1 117.4 (4) C23—C24—C26 121.6 (4)

C2—C1—S1 121.0 (3) C25—C24—C26 118.9 (4)

C6—C5—C4 121.1 (4) C19—C25—C24 121.3 (4)

C5—C4—C3 118.8 (5) C22—C23—C24 119.7 (5)

C5—C4—C7 120.3 (5) C23—C22—C20 121.2 (5)

C3—C4—C7 120.9 (5) O5—C20—C22 124.7 (4)

C1—C6—C5 118.7 (5) O5—C20—C19 115.1 (4)

C3—C2—C1 120.3 (4) C22—C20—C19 120.2 (4)

C2—C3—C4 119.8 (5) C20—O5—C21 116.8 (4)

O2—C8—C13 106.5 (3) O7—C27—O6 123.7 (4)

O2—C8—C9 108.8 (4) O7—C27—C26 126.1 (5)


SI-‐14

C13—C8—C9 112.1 (4) O6—C27—C26 110.2 (4)

O10—C11—O2 121.4 (6) N1—C26—C27 111.6 (4)

O10—C11—C12 127.3 (5) N1—C26—C24 107.4 (4)

O2—C11—C12 111.3 (6) C27—C26—C24 108.5 (3)

C8—C9—S1 109.3 (3) C27—O6—C28 115.2 (4)

C11—O2—C8 117.5 (4) C29—N1—C26 118.7 (4)

C16—C17—C13 119.0 (4) C29—O9—C31 120.5 (4)

C16—C15—C36 118.8 (3) O8—C29—N1 124.9 (5)

C14—C13—C17 121.4 (3) O8—C29—O9 126.6 (5)

C14—C13—C8 120.4 (4) N1—C29—O9 108.6 (5)

C17—C13—C8 118.2 (4) O9—C31—C32 101.7 (5)

O3—C16—C17 114.0 (4) O9—C31—C33 109.2 (5)

O3—C16—C15 124.7 (3) C32—C31—C33 110.4 (5)

C17—C16—C15 121.3 (4) O9—C31—C34 109.8 (4)

C13—C14—C36 117.6 (4) C32—C31—C34 112.7 (6)

C13—C14—C19 121.2 (3) C33—C31—C34 112.4 (6)

C36—C14—C19 121.1 (4) O4—C36—C15 123.0 (3)

C16—O3—C37 118.9 (4) O4—C36—C14 115.0 (4)

C36—O4—C18 117.5 (4) C15—C36—C14 121.9 (4)


SI-‐15

aS-5:

Crystal data

Mr = 627.73 Mo Kα radiation, λ = 0.71073 Å

Monoclinic, P21

Cell parameters from 9970 reflections

Hall symbol: P 2yb θ = 2.7–28.0°

a = 10.6718 (5) Å µ = 0.15 mm−1

b = 11.6816 (6) Å T = 173 K

c = 14.2167 (7) Å Prism, colourless

β = 111.935 (1)° 0.30 × 0.20 × 0.15 mm

V = 1644.01 (14) Å3 F(000) = 668

Z = 2

Data collection


SI-‐16

Radiation source: fine-focus sealed tube

5867 reflections with I > 2σ(I)

graphite Rint = 0.016

θmax = 28.0°, θmin = 2.1°

φ and ω scans h = −14 14

Absorption correction: multi-scan SADABS

k = −7 15

Tmin = 0.956, Tmax = 0.978 l = −18 18

17874 measured reflections

Refinement

wR(F2) = 0.069 Δρmax = 0.18 e Å−3

S = 1.05 Δρmin = −0.19 e Å−3

6187 reflections Flack parameter: 0.01 (4)

410 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

C1 0.91622 (14) 1.10812 (13) 0.82225 (10) 0.0215 (3)

C2 0.83951 (17) 1.20070 (14) 0.82934 (12) 0.0287 (3)

H2 0.8758 1.2553 0.8821 0.034*

C3 0.70966 (18) 1.21304 (16) 0.75887 (12) 0.0351 (4)

H3 0.6559 1.2755 0.7645 0.042*

C4 0.65644 (17) 1.13532 (18) 0.67965 (12) 0.0363 (4)

C5 0.73597 (17) 1.04451 (17) 0.67357 (13) 0.0374 (4)

H5 0.7013 0.9913 0.6194 0.045*

C6 0.86569 (16) 1.02943 (15) 0.74505 (12) 0.0303 (3)

H6 0.9188 0.9658 0.7408 0.036*

C7 0.5166 (2) 1.1506 (3) 0.59985 (16) 0.0619 (7)

H7A 0.5186 1.1346 0.5328 0.093*


SI-‐17

H7B 0.4864 1.2295 0.6017 0.093*

H7C 0.4540 1.0977 0.6133 0.093*

C8 1.05493 (14) 1.00053 (14) 1.00288 (10) 0.0231 (3)

H8A 1.0305 0.9234 0.9726 0.028*

H8B 1.1401 0.9929 1.0627 0.028*

C9 0.94541 (13) 1.04028 (13) 1.03897 (10) 0.0190 (3)

H9 0.8572 1.0399 0.9800 0.023*

C10 0.86026 (15) 1.20833 (15) 1.08664 (12) 0.0283 (3)

H10A 0.7870 1.2154 1.0201 0.043*

H10B 0.8852 1.2845 1.1167 0.043*

H10C 0.8301 1.1609 1.1310 0.043*

C11 0.93401 (14) 0.96144 (12) 1.12061 (10) 0.0183 (3)

C12 1.03994 (14) 0.96086 (13) 1.21616 (10) 0.0209 (3)

H12 1.1170 1.0080 1.2288 0.025*

C13 1.03042 (15) 0.89088 (14) 1.29129 (10) 0.0224 (3)

C14 0.91486 (15) 0.82569 (14) 1.27485 (10) 0.0234 (3)

H14 0.9078 0.7798 1.3278 0.028*

C15 0.81037 (14) 0.82806 (13) 1.18090 (10) 0.0201 (3)

C16 0.82012 (13) 0.89377 (12) 1.10073 (10) 0.0170 (3)

C17 1.25305 (16) 0.93735 (17) 1.40733 (12) 0.0339 (4)

H17A 1.2921 0.9147 1.3577 0.051*

H17B 1.3157 0.9174 1.4757 0.051*

H17C 1.2371 1.0201 1.4031 0.051*

C18 0.67751 (18) 0.70504 (16) 1.23943 (13) 0.0337 (4)

H18A 0.7466 0.6450 1.2618 0.050*

H18B 0.5876 0.6700 1.2158 0.050*

H18C 0.6878 0.7566 1.2962 0.050*

C19 0.70993 (13) 0.88695 (12) 0.99797 (10) 0.0177 (3)

C20 0.58835 (14) 0.94555 (13) 0.97818 (11) 0.0219 (3)


SI-‐18

C21 0.48418 (14) 0.93683 (14) 0.88379 (11) 0.0254 (3)

H21 0.4001 0.9736 0.8714 0.031*

C22 0.50425 (14) 0.87380 (14) 0.80778 (11) 0.0234 (3)

H22 0.4336 0.8693 0.7429 0.028*

C23 0.62537 (13) 0.81708 (13) 0.82440 (10) 0.0190 (3)

C24 0.72635 (13) 0.82324 (12) 0.92086 (10) 0.0177 (3)

H24 0.8085 0.7828 0.9342 0.021*

C25 0.47876 (18) 1.0950 (2) 1.03259 (14) 0.0466 (5)

H25A 0.4794 1.1414 0.9754 0.070*

H25B 0.4949 1.1443 1.0917 0.070*

H25C 0.3908 1.0573 1.0145 0.070*

C26 0.64184 (13) 0.74743 (13) 0.73918 (10) 0.0209 (3)

H26 0.5855 0.7843 0.6735 0.025*

C27 0.58800 (14) 0.62658 (14) 0.73951 (11) 0.0253 (3)

C28 0.3912 (2) 0.5117 (2) 0.6877 (2) 0.0575 (6)

H28A 0.4332 0.4541 0.6587 0.086*

H28B 0.2945 0.5165 0.6466 0.086*

H28C 0.4038 0.4898 0.7572 0.086*

C29 0.80665 (14) 0.75644 (13) 0.65892 (10) 0.0217 (3)

C30 0.99808 (15) 0.76790 (17) 0.60288 (12) 0.0306 (3)

C31 0.9534 (3) 0.87996 (19) 0.54759 (17) 0.0509 (6)

H31A 0.8557 0.8779 0.5090 0.076*

H31B 1.0006 0.8920 0.5010 0.076*

H31C 0.9748 0.9428 0.5968 0.076*

C32 1.14795 (19) 0.7699 (3) 0.66459 (16) 0.0688 (8)

H32A 1.1687 0.8330 0.7134 0.103*

H32B 1.1973 0.7806 0.6194 0.103*

H32C 1.1750 0.6972 0.7011 0.103*

C33 0.9599 (2) 0.66623 (18) 0.53226 (14) 0.0414 (4)


SI-‐19

H33A 0.9815 0.5954 0.5721 0.062*

H33B 1.0107 0.6687 0.4873 0.062*

H33C 0.8629 0.6686 0.4915 0.062*

N1 0.77975 (11) 0.74352 (12) 0.74419 (9) 0.0217 (3)

O1 1.15693 (11) 1.01543 (12) 0.86184 (8) 0.0324 (3)

O2 0.97551 (10) 1.15579 (9) 1.07503 (7) 0.0217 (2)

O3 1.12840 (11) 0.87885 (11) 1.38614 (8) 0.0303 (3)

O4 0.69283 (10) 0.76829 (11) 1.15875 (8) 0.0280 (2)

O5 0.58233 (10) 1.01042 (11) 1.05613 (8) 0.0294 (2)

O6 0.65459 (12) 0.54527 (11) 0.78045 (10) 0.0374 (3)

O7 0.45409 (11) 0.62277 (12) 0.68861 (10) 0.0411 (3)

O8 0.72162 (11) 0.77061 (13) 0.57481 (8) 0.0341 (3)

O9 0.94078 (10) 0.75336 (11) 0.68253 (7) 0.0263 (2)

S1 1.08647 (3) 1.09252 (3) 0.91072 (3) 0.02316 (8)

H1N 0.8444 (17) 0.7201 (15) 0.7988 (13) 0.022 (4)*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

C1 0.0245 (6) 0.0228 (7) 0.0183 (6) −0.0028 (6) 0.0090 (5) 0.0024 (5)

C2 0.0407 (9) 0.0235 (8) 0.0230 (7) 0.0026 (7) 0.0130 (6) 0.0003 (6)

C3 0.0419 (9) 0.0359 (10) 0.0298 (8) 0.0130 (8) 0.0160 (7) 0.0062 (7)

C4 0.0307 (8) 0.0478 (11) 0.0276 (7) 0.0074 (8) 0.0076 (6) 0.0043 (7)

C5 0.0360 (9) 0.0398 (10) 0.0281 (8) 0.0011 (8) 0.0025 (7) −0.0083 (7)

C6 0.0328 (8) 0.0268 (9) 0.0292 (8) 0.0034 (7) 0.0091 (6) −0.0045 (6)

C7 0.0392 (11) 0.092 (2) 0.0393 (10) 0.0231 (12) −0.0022 (8) −0.0056 (11)

C8 0.0242 (7) 0.0251 (7) 0.0197 (6) 0.0001 (6) 0.0078 (5) 0.0037 (6)

C9 0.0186 (6) 0.0217 (7) 0.0158 (6) −0.0024 (5) 0.0054 (5) 0.0014 (5)

C10 0.0280 (8) 0.0268 (8) 0.0313 (8) 0.0028 (6) 0.0124 (6) 0.0003 (6)

C11 0.0197 (6) 0.0189 (7) 0.0172 (6) 0.0012 (5) 0.0077 (5) 0.0005 (5)


SI-‐20

C12 0.0185 (6) 0.0241 (7) 0.0186 (6) −0.0028 (5) 0.0051 (5) 0.0002 (5)

C13 0.0242 (7) 0.0278 (8) 0.0146 (6) 0.0016 (6) 0.0066 (5) −0.0006 (5)

C14 0.0285 (7) 0.0256 (7) 0.0186 (6) −0.0002 (6) 0.0117 (5) 0.0035 (6)

C15 0.0216 (6) 0.0202 (7) 0.0210 (6) −0.0004 (5) 0.0110 (5) −0.0013 (5)

C16 0.0166 (6) 0.0190 (7) 0.0161 (6) 0.0014 (5) 0.0070 (5) −0.0009 (5)

C17 0.0270 (8) 0.0440 (10) 0.0223 (7) −0.0045 (7) −0.0004 (6) 0.0019 (7)

C18 0.0366 (9) 0.0371 (10) 0.0329 (8) −0.0116 (7) 0.0194 (7) 0.0016 (7)

C19 0.0155 (6) 0.0196 (7) 0.0176 (6) −0.0002 (5) 0.0056 (5) 0.0015 (5)

C20 0.0199 (7) 0.0231 (7) 0.0238 (7) 0.0016 (6) 0.0094 (5) −0.0012 (6)

C21 0.0165 (6) 0.0315 (8) 0.0274 (7) 0.0047 (6) 0.0072 (6) −0.0011 (6)

C22 0.0173 (6) 0.0290 (8) 0.0205 (6) 0.0007 (6) 0.0031 (5) −0.0005 (6)

C23 0.0169 (6) 0.0210 (7) 0.0193 (6) −0.0026 (5) 0.0069 (5) 0.0004 (5)

C24 0.0145 (6) 0.0189 (7) 0.0200 (6) 0.0011 (5) 0.0067 (5) 0.0019 (5)

C25 0.0409 (9) 0.0548 (12) 0.0385 (9) 0.0269 (10) 0.0083 (7) −0.0125 (9)

C26 0.0161 (6) 0.0274 (8) 0.0174 (6) −0.0004 (6) 0.0040 (5) −0.0011 (6)

C27 0.0210 (7) 0.0301 (8) 0.0256 (7) −0.0039 (6) 0.0097 (5) −0.0097 (6)

C28 0.0392 (10) 0.0478 (13) 0.0797 (16) −0.0221 (10) 0.0156 (10) −0.0218 (12)

C29 0.0234 (6) 0.0212 (7) 0.0209 (6) −0.0016 (6) 0.0086 (5) −0.0031 (6)

C30 0.0316 (8) 0.0422 (10) 0.0263 (7) −0.0034 (7) 0.0203 (6) −0.0013 (7)

C31 0.0836 (16) 0.0339 (11) 0.0584 (12) −0.0032 (10) 0.0533 (12) 0.0030 (9)

C32 0.0326 (10) 0.140 (3) 0.0433 (11) −0.0076 (14) 0.0254 (9) −0.0059 (14)

C33 0.0651 (13) 0.0343 (10) 0.0382 (9) 0.0032 (9) 0.0346 (9) −0.0024 (8)

N1 0.0163 (5) 0.0326 (7) 0.0157 (5) −0.0001 (5) 0.0055 (4) 0.0001 (5)

O1 0.0280 (5) 0.0440 (7) 0.0304 (6) 0.0028 (5) 0.0169 (4) 0.0004 (5)

O2 0.0217 (5) 0.0206 (5) 0.0223 (5) −0.0023 (4) 0.0075 (4) 0.0002 (4)

O3 0.0273 (5) 0.0425 (7) 0.0165 (5) −0.0044 (5) 0.0029 (4) 0.0054 (5)

O4 0.0262 (5) 0.0326 (6) 0.0260 (5) −0.0087 (5) 0.0106 (4) 0.0031 (5)

O5 0.0260 (5) 0.0361 (7) 0.0253 (5) 0.0104 (5) 0.0088 (4) −0.0055 (5)

O6 0.0318 (6) 0.0290 (6) 0.0527 (7) 0.0001 (5) 0.0175 (5) −0.0001 (6)


SI-‐21

O7 0.0213 (5) 0.0405 (8) 0.0537 (7) −0.0096 (5) 0.0050 (5) −0.0110 (6)

O8 0.0288 (5) 0.0531 (8) 0.0185 (5) 0.0024 (6) 0.0068 (4) 0.0019 (5)

O9 0.0219 (5) 0.0403 (7) 0.0200 (5) −0.0006 (5) 0.0115 (4) 0.0009 (5)

S1 0.02238 (15) 0.02724 (18) 0.02134 (15) −0.00511 (15) 0.00987 (12) −0.00031 (14)

Geometric parameters (Å, °)

C1—C6 1.378 (2) C18—H18C 0.9800

C1—C2 1.383 (2) C19—C24 1.3892 (19)

C1—S1 1.7914 (14) C19—C20 1.3994 (19)

C2—C3 1.381 (2) C20—O5 1.3637 (18)

C2—H2 0.9500 C20—C21 1.390 (2)

C3—C4 1.392 (3) C21—C22 1.389 (2)

C3—H3 0.9500 C21—H21 0.9500

C4—C5 1.381 (3) C22—C23 1.392 (2)

C4—C7 1.511 (2) C22—H22 0.9500

C5—C6 1.389 (2) C23—C24 1.3939 (18)

C5—H5 0.9500 C23—C26 1.5230 (19)

C6—H6 0.9500 C24—H24 0.9500

C7—H7A 0.9800 C25—O5 1.426 (2)

C7—H7B 0.9800 C25—H25A 0.9800

C7—H7C 0.9800 C25—H25B 0.9800

C8—C9 1.514 (2) C25—H25C 0.9800

C8—S1 1.8205 (15) C26—N1 1.4474 (17)

C8—H8A 0.9900 C26—C27 1.525 (2)

C8—H8B 0.9900 C26—H26 1.0000

C9—O2 1.4366 (18) C27—O6 1.199 (2)

C9—C11 1.5217 (19) C27—O7 1.3399 (17)

C9—H9 1.0000 C28—O7 1.459 (3)

C10—O2 1.4381 (18) C28—H28A 0.9800


SI-‐22

C10—H10A 0.9800 C28—H28B 0.9800

C10—H10B 0.9800 C28—H28C 0.9800

C10—H10C 0.9800 C29—O8 1.2125 (17)

C11—C16 1.3875 (19) C29—O9 1.3431 (16)

C11—C12 1.4058 (18) C29—N1 1.3545 (18)

C12—C13 1.378 (2) C30—O9 1.4840 (17)

C12—H12 0.9500 C30—C33 1.509 (3)

C13—O3 1.3703 (16) C30—C31 1.510 (3)

C13—C14 1.393 (2) C30—C32 1.510 (2)

C14—C15 1.3840 (19) C31—H31A 0.9800

C14—H14 0.9500 C31—H31B 0.9800

C15—O4 1.3657 (17) C31—H31C 0.9800

C15—C16 1.4099 (19) C32—H32A 0.9800

C16—C19 1.4967 (18) C32—H32B 0.9800

C17—O3 1.424 (2) C32—H32C 0.9800

C17—H17A 0.9800 C33—H33A 0.9800

C17—H17B 0.9800 C33—H33B 0.9800

C17—H17C 0.9800 C33—H33C 0.9800

C18—O4 1.4242 (19) N1—H1N 0.868 (18)

C18—H18A 0.9800 O1—S1 1.4998 (12)

C18—H18B 0.9800

C6—C1—C2 120.92 (14) O5—C20—C21 124.17 (13)

C6—C1—S1 118.94 (12) O5—C20—C19 115.47 (12)

C2—C1—S1 120.08 (11) C21—C20—C19 120.35 (13)

C3—C2—C1 119.32 (15) C22—C21—C20 119.32 (13)

C3—C2—H2 120.3 C22—C21—H21 120.3

C1—C2—H2 120.3 C20—C21—H21 120.3

C2—C3—C4 120.96 (16) C21—C22—C23 121.58 (13)

C2—C3—H3 119.5 C21—C22—H22 119.2


SI-‐23

C4—C3—H3 119.5 C23—C22—H22 119.2

C5—C4—C3 118.49 (15) C22—C23—C24 118.04 (13)

C5—C4—C7 120.12 (18) C22—C23—C26 119.68 (12)

C3—C4—C7 121.37 (18) C24—C23—C26 122.25 (12)

C4—C5—C6 121.29 (16) C19—C24—C23 121.66 (12)

C4—C5—H5 119.4 C19—C24—H24 119.2

C6—C5—H5 119.4 C23—C24—H24 119.2

C1—C6—C5 119.00 (15) O5—C25—H25A 109.5

C1—C6—H6 120.5 O5—C25—H25B 109.5

C5—C6—H6 120.5 H25A—C25—H25B 109.5

C4—C7—H7A 109.5 O5—C25—H25C 109.5

C4—C7—H7B 109.5 H25A—C25—H25C 109.5

H7A—C7—H7B 109.5 H25B—C25—H25C 109.5

C4—C7—H7C 109.5 N1—C26—C23 113.27 (11)

H7A—C7—H7C 109.5 N1—C26—C27 110.37 (12)

H7B—C7—H7C 109.5 C23—C26—C27 109.67 (11)

C9—C8—S1 115.88 (11) N1—C26—H26 107.8

C9—C8—H8A 108.3 C23—C26—H26 107.8

S1—C8—H8A 108.3 C27—C26—H26 107.8

C9—C8—H8B 108.3 O6—C27—O7 123.73 (15)

S1—C8—H8B 108.3 O6—C27—C26 125.40 (13)

H8A—C8—H8B 107.4 O7—C27—C26 110.87 (13)

O2—C9—C8 108.11 (11) O7—C28—H28A 109.5

O2—C9—C11 111.55 (11) O7—C28—H28B 109.5

C8—C9—C11 111.38 (12) H28A—C28—H28B 109.5

O2—C9—H9 108.6 O7—C28—H28C 109.5

C8—C9—H9 108.6 H28A—C28—H28C 109.5

C11—C9—H9 108.6 H28B—C28—H28C 109.5

O2—C10—H10A 109.5 O8—C29—O9 125.81 (13)


SI-‐24

O2—C10—H10B 109.5 O8—C29—N1 124.56 (13)

H10A—C10—H10B 109.5 O9—C29—N1 109.62 (11)

O2—C10—H10C 109.5 O9—C30—C33 109.38 (14)

H10A—C10—H10C 109.5 O9—C30—C31 110.87 (14)

H10B—C10—H10C 109.5 C33—C30—C31 112.44 (15)

C16—C11—C12 121.40 (13) O9—C30—C32 101.97 (12)

C16—C11—C9 120.20 (12) C33—C30—C32 111.24 (19)

C12—C11—C9 118.39 (12) C31—C30—C32 110.5 (2)

C13—C12—C11 119.09 (13) C30—C31—H31A 109.5

C13—C12—H12 120.5 C30—C31—H31B 109.5

C11—C12—H12 120.5 H31A—C31—H31B 109.5

O3—C13—C12 124.98 (14) C30—C31—H31C 109.5

O3—C13—C14 114.29 (13) H31A—C31—H31C 109.5

C12—C13—C14 120.73 (13) H31B—C31—H31C 109.5

C15—C14—C13 119.65 (13) C30—C32—H32A 109.5

C15—C14—H14 120.2 C30—C32—H32B 109.5

C13—C14—H14 120.2 H32A—C32—H32B 109.5

O4—C15—C14 123.50 (13) C30—C32—H32C 109.5

O4—C15—C16 115.52 (12) H32A—C32—H32C 109.5

C14—C15—C16 120.99 (13) H32B—C32—H32C 109.5

C11—C16—C15 117.98 (12) C30—C33—H33A 109.5

C11—C16—C19 122.56 (12) C30—C33—H33B 109.5

C15—C16—C19 119.46 (12) H33A—C33—H33B 109.5

O3—C17—H17A 109.5 C30—C33—H33C 109.5

O3—C17—H17B 109.5 H33A—C33—H33C 109.5

H17A—C17—H17B 109.5 H33B—C33—H33C 109.5

O3—C17—H17C 109.5 C29—N1—C26 120.26 (11)

H17A—C17—H17C 109.5 C29—N1—H1N 118.2 (11)

H17B—C17—H17C 109.5 C26—N1—H1N 120.5 (11)


SI-‐25

O4—C18—H18A 109.5 C9—O2—C10 110.79 (11)

O4—C18—H18B 109.5 C13—O3—C17 117.91 (12)

H18A—C18—H18B 109.5 C15—O4—C18 116.83 (12)

O4—C18—H18C 109.5 C20—O5—C25 117.51 (12)

H18A—C18—H18C 109.5 C27—O7—C28 115.37 (15)

H18B—C18—H18C 109.5 C29—O9—C30 120.71 (11)

C24—C19—C20 118.96 (12) O1—S1—C1 106.76 (7)

C24—C19—C16 120.94 (12) O1—S1—C8 103.79 (7)

C20—C19—C16 120.10 (12) C1—S1—C8 98.84 (6)

C6—C1—C2—C3 1.1 (2) C19—C20—C21—C22 −3.0 (2)

S1—C1—C2—C3 178.28 (12) C20—C21—C22—C23 1.3 (2)

C1—C2—C3—C4 −1.6 (3) C21—C22—C23—C24 1.3 (2)

C2—C3—C4—C5 0.7 (3) C21—C22—C23—C26 179.02 (15)

C2—C3—C4—C7 −177.56 (19) C20—C19—C24—C23 0.5 (2)

C3—C4—C5—C6 0.7 (3) C16—C19—C24—C23 −179.23 (13)

C7—C4—C5—C6 179.00 (19) C22—C23—C24—C19 −2.2 (2)

C2—C1—C6—C5 0.3 (2) C26—C23—C24—C19 −179.89 (13)

S1—C1—C6—C5 −176.93 (14) C22—C23—C26—N1 149.90 (14)

C4—C5—C6—C1 −1.2 (3) C24—C23—C26—N1 −32.43 (19)

S1—C8—C9—O2 −53.38 (13) C22—C23—C26—C27 −86.31 (16)

S1—C8—C9—C11 −176.27 (10) C24—C23—C26—C27 91.36 (15)

O2—C9—C11—C16 127.12 (13) N1—C26—C27—O6 30.6 (2)

C8—C9—C11—C16 −111.98 (14) C23—C26—C27—O6 −94.92 (17)

O2—C9—C11—C12 −51.72 (17) N1—C26—C27—O7 −150.36 (12)

C8—C9—C11—C12 69.18 (17) C23—C26—C27—O7 84.17 (14)

C16—C11—C12—C13 0.4 (2) O8—C29—N1—C26 −0.7 (2)

C9—C11—C12—C13 179.26 (13) O9—C29—N1—C26 178.07 (13)

C11—C12—C13—O3 177.32 (14) C23—C26—N1—C29 −136.89 (14)

C11—C12—C13—C14 −3.1 (2) C27—C26—N1—C29 99.71 (16)


SI-‐26

O3—C13—C14—C15 −178.12 (13) C8—C9—O2—C10 165.65 (11)

C12—C13—C14—C15 2.3 (2) C11—C9—O2—C10 −71.56 (13)

C13—C14—C15—O4 −178.95 (14) C12—C13—O3—C17 −4.0 (2)

C13—C14—C15—C16 1.3 (2) C14—C13—O3—C17 176.40 (15)

C12—C11—C16—C15 3.0 (2) C14—C15—O4—C18 2.9 (2)

C9—C11—C16—C15 −175.80 (13) C16—C15—O4—C18 −177.35 (14)

C12—C11—C16—C19 −175.98 (13) C21—C20—O5—C25 −15.9 (2)

C9—C11—C16—C19 5.2 (2) C19—C20—O5—C25 163.21 (16)

O4—C15—C16—C11 176.34 (13) O6—C27—O7—C28 1.5 (2)

C14—C15—C16—C11 −3.9 (2) C26—C27—O7—C28 −177.63 (15)

O4—C15—C16—C19 −4.63 (19) O8—C29—O9—C30 0.0 (3)

C14—C15—C16—C19 175.15 (13) N1—C29—O9—C30 −178.78 (14)

C11—C16—C19—C24 76.41 (19) C33—C30—O9—C29 −67.4 (2)

C15—C16—C19—C24 −102.57 (16) C31—C30—O9—C29 57.2 (2)

C11—C16—C19—C20 −103.34 (16) C32—C30—O9—C29 174.78 (19)

C15—C16—C19—C20 77.68 (18) C6—C1—S1—O1 18.54 (14)

C24—C19—C20—O5 −177.05 (13) C2—C1—S1—O1 −158.68 (12)

C16—C19—C20—O5 2.7 (2) C6—C1—S1—C8 −88.85 (13)

C24—C19—C20—C21 2.1 (2) C2—C1—S1—C8 93.93 (13)

C16—C19—C20—C21 −178.12 (14) C9—C8—S1—O1 −159.99 (10)

O5—C20—C21—C22 176.07 (15) C9—C8—S1—C1 −50.19 (12)

Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A

N1—H1N···O2i 0.868 (18) 2.213 (18) 3.0760 (15) 172.4 (15)

Symmetry code: (i) −x+2, y−1/2, −z+2.


Date post:	18-Jan-2021
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Supporting Information Construction of the biaryl-part of … · 2012. 4. 3. · SI#1% % Supporting...

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