Baran Lab Group Meeting 02.13.16 Justine deGruyter Three-Membered Heterocycles Containing Two (or more) Heteroatoms P P R 1 R diphosphiranes R 3 R 2 P P N(iPr) 2 (iPr) 2 N P P P P N(iPr) 2 (iPr) 2 N Et 3 N, BF 3 • THF Bertrand, G. Science. 1999, 279, 2080. P P Me R Me R N 2 TMS Et 2 O R P P TMS R Me Me Me Me R = Zeitschrift fuer Angorganische. 1992, 610, 75. (via SciFinder) Photoreactive cross-linking. R R 1 N N R R 1 - N 2 - when R, R 1 are e - -donating: singlet carbene - when R, R 1 are e - -withdrawing: triplet carbene N H O OR Me O O Me N N 1,2 Balas, L. J. Med. Chem. 2009, 52, 1005. h υ Me Me OTBDMS N N CF 3 m-azipropofol Eckenhoff, R.G. J. Med. Chem. 2010, 53, 5667. N O O O O Me N N ThermoScientific spacer arm: 3.9 Å N O O O O ThermoScientific spacer arm: 12.5 Å S S NH O Me N N NaO 3 S S S R 1 R dithiiranes O Ph Me Me Me Me Ph O S S Ph Ph Ph Ph Ph Ph Me Me Me Me S S Ph Me Me Me Me S S Ph Ph Ph exo, 35% endo, 57% Oxone, KOH [MeN(C 8 H 17 ) 3 ]Cl Ph S S Ph O Me Me Me Me mCPBA Nakayama, J. Pure and Appl. Chem. 1996, 68, 869. "diathiavermilione" exo --> cis, 57%; endo --> trans, 2% O O O S R R S thiosulfines isomeric FG S—S: 2.073Å C—S: 1.821Å, 1.814Å Key references. J. Am. Chem. Soc. 1977, 99, 2931.; J. Org. Chem. 2002, 67, 5690.; Pure and Appl. Chem. 1999, 68, 869. - stability arises from bulky substituents - no examples of electronically stabilized (as of 2002) Me Me R R SO Me Me Me R R S Me S Me Me R R Me S S Lawesson's Rgt Shimada, K. Chem. Lett. 1999, 695. diazirines N N R 1 R R R 1 O R R 1 NH HN R R 1 N N 1. NH 2 OH•HCl, py. 2. TsCl, Et 3 N 3. NH 3 CrO 3 , H 2 SO 4 Graham Reaction. J. Am. Chem. Soc. 1965, 87, 4396. NH NH 2 R NaOX X = Br, Cl R X N N R X 1 N N TBAX' X' = F, OMe, N 3 (CN), etc. Preparation. Key references. Acc. Chem. Res. 2006, 39, 267.; J. Org. Chem. 1970, 35, 2465.; Arkivoc. 2008, 128. Primary uses. carbene chemistry, photoreactive cross-linking (preferred for small size, long irradiation wavelength, short required irradiation times, stability in the presence of various nucleophiles, and stability at various pH levels)
Transcript
Baran Lab Group Meeting02.13.16Justine deGruyter
Three-Membered Heterocycles Containing Two (or more)Heteroatoms
Key references. J. Am. Chem. Soc. 1977, 99, 2931.; J. Org. Chem. 2002, 67, 5690.; Pure and Appl. Chem.1999, 68, 869.- stability arises from bulky substituents- no examples of electronically stabilized (as of 2002)
Me MeR
R
SOMe
Me MeR
R
SMe
S
Me MeR
RMe
S S
Lawesson's Rgt
Shimada, K. Chem. Lett. 1999, 695.
diazirines
N N
R1R
R R1
O
R R1
NHHN
R R1
NN1. NH2OH•HCl, py.
2. TsCl, Et3N3. NH3
CrO3, H2SO4
Graham Reaction. J. Am. Chem. Soc. 1965, 87, 4396.
NH
NH2R
NaOX
X = Br, Cl R X
NN
R X1
NNTBAX'
X' = F, OMe, N3 (CN), etc.
Preparation.
Key references. Acc. Chem. Res. 2006, 39, 267.; J. Org. Chem.1970, 35, 2465.; Arkivoc. 2008, 128.Primary uses. carbene chemistry, photoreactive cross-linking (preferred for small size, long irradiation wavelength, short required irradiation times, stability in the presence of various nucleophiles, and stability at various pH levels)
Baran Lab Group Meeting02.13.16Justine deGruyter
Three-Membered Heterocycles Containing Two (or more)Heteroatoms
OO
MeMe
dimethyldioxirane (DMDO)
OHO
Me
OTBDPS
OEt
OMe
OTBDPS
OHO SEtMe
OO
NOHO
Overman, L.E. J. Am. Chem. Soc. 2010, 132 , 7876.
(+)-sieboldine A
1. DMDO, CH2Cl2
2. BF3 OEt2, EtSH, CH2Cl2, 53%
Preparation.
Me
O
Me
O O
MeMe
Oxone
NaHCO3, H2O20 L
batch process
OO
R1R
Key References.Chem Rev. 1989, 89, 1187.; Acc. Chem. Res. 1989, 22, 205. Pure and Appl. Chem. 1995, 65, 811.
