Kinetic Resolutions - The Stoltz Group

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(±)- NHAc Miller Peptide Catalyst - Round 2 OH NHAc N N 2 mol% Catalyst 8 4.8 eq Ac 2 O PhCH 3 , 0 o C N Boc OH OH N H NHAc O O N H O Catalyst 8 H N OMe O Bn OAc NHAc OH NHAc s = 28 Miller has extended this hairpin turn structure to an octapeptide, which shows improved selectivities for this class of substrates: s = 51 s = 15 s = 27 Miller, et. al., J. Am. Chem. Soc., 1999, 121, 11638 10
CO2R PPh3 N N RO2C RO2C CO2R HN NH Mitsunobu-type KR of ROH Ph3P CO2R R N N RO2C 2 CO2H Step 1 Step 2 Ph3PO R 2 CO 2R 3 Chiral recognition can be introduced at steps 3 and 4 Step 4 Ph 3 PO-R R 2 - CO2 Ph 3 P RO 2C RO2C CO2R N NH R 3 OH Step 3 CO2R HN NH Chiral Phosphine, azodicarboxylate, or acid are possible means to induce chiral influence Kellogg Tang (±)- (±)- Ar Ar OH OH 1-2 eq Catalyst 9 O R + NH Catalyst 9 1-2 eq ArCO 2H DIAD, PhH 1 eq 1 eq Chiral Phosphines for Mitsunobu KR O O O P NMe 2 Ar OH + 1) 1 eq Catalyst 9 DEAD, THF Reflux 2) NH 2 NH 2 DIAD, PhH Ar Ar OCOAr OH 40-50% R 13-30% ee R 2 - CO2 Chandrasekhar, Tet. Asym. 2002, 13, 615 Ar = Ph, 2-Naphthyl 14-73% conv. 11-39% ee + Ar NH 2 55-62% R 26-45% ee Me2N O P O O N N CO 2i-Pr Oi-Pr Kellogg, et. al., J. Chem. Soc., Perkin Trans. 1, 1995, 2961 Tang, et. al., Tet. Asym., 2002, 13, 145 11
Page 1 and 2: N Me N Kinetic Resolutions Episode
Page 3 and 4: (±)- Evans - Oxazolidinone Acylati
Page 5 and 6: Cl (±)- R 1 R 1 = Ar OH R 2 R 2 =
Page 7 and 8: (±)- (±)- Et 3N Me (±)- Ph Ph OH
Page 9: BocHN (±)- N N Tripeptides for Acy
Page 13 and 14: Nishiyama, Sekar (our very own!) n
Page 15 and 16: t-Bu R 3 OH R 1 R 1 R 1 (±)- + + R
Page 17 and 18: (±)- Gardiner (±)- (±)- MeO 2C P
Page 19 and 20: Sharpless Et t-Bu Proposed Asymmetr
Page 21: R (CH2)3CH3 CH 3 (CH2)11CH3 (CH 2 )

Kinetic Resolutions - The Stoltz Group

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