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Massachusetts Institute of TechnologyOrganic Chemistry 5.512
December 3, 2007Prof. Rick L. Danheiser
Unit 6
Stereocontrolled Aldol Reactions
Overview of the Stereochemistry of the Aldol Reaction and Substrate Control
Reagent Control: Chiral Auxiliary Strategies
Reagent Control: Chiral Controller Strategies
Reagent Control: Chiral Lewis Acid Catalyzed Aldol Reactions
David A. EvansSatoru Masamune Clayton H. Heathcock
Lecture 18
R1OH
R2
O
Z234
The Aldol Retron
Alexsander Borodin
General References on Aldol Chemistry
"Catalyzed Enantioselective Aldol Additions of Latent Enolate Equivalents"Nelson, S. G. Tetrahedron: Asymmetry 1998, 9, 357-389.
"Diastereoselection in Lewis-Acid-Mediated Aldol Additions"Mahrwald, R. Chem. Rev. 1999, 99, 1095-1120.
"The Catalytic Asymmetric Aldol Reaction"Machajewski, T. D.; Wong, C.-H. Angew. Chem. Int. Ed. 2000, 39, 1352-1374.
"Recent Developments in Asymmetric Aldol Methodology"Franklin, A. S.; Paterson, I. Contemp. Org. Syn. 1994, 1, 317-338.
"Asymmetric Aldol Reactions Using Boron Enolates"Cowden, C. J.; Paterson, I. Org. React. 1997, 51, 1.
"Recent Advances in Asymmetric Aldol Addition Reactions"Carreira, E. M. In Catalytic Asymmetric Synthesis, Second Edition; Ojima, I., Ed.; Wiley-VCH, 2000, pp 513-541.
"Aldol Reactions: Methodology and Stereochemistry"Carreira, E. M. In Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH, 2000, pp 227-248.
"Stereoselective Aldol Reactions in the Synthesis of Polyketide Natural Products"Paterson, I.; Cowden, C. J.; Wallace, D. J.; In Modern Carbonyl Chemistry; Otera, J., Ed.; Wiley-VCH, 2000, pp 249-298.
Modern Aldol Reactions (2 Vols); Mahrwald, R., Ed.; Wiley-VCH, 2004.
"Current Progress in the Asymmetric Aldol Addition Reaction"Palomo, C.; Oiarbide, M.; Garcia, J. M. Chem. Soc. Rev. 2004, 33, 65.
"Catalytic Enantioselective Aldol Addition Reactions"Carreira, E. M.; Fettes, A.; Marti, C.Org. React. 2006, 67, 1.
"Modern Aldol Methods for the Total Synthesis of Polyketides"Schetter, B.; Mahrwald, R.Angew. Chem. Int. Ed. 2006, 45, 7506
Aldol Reaction Stereochemistry: Recent Examples
Evans, D. A.; Siska, S. A.; Cee, V. J. Angew. Chem. Int. Ed. 2003, 42, 1761. See alsoEvans, D. A. et. al J. Am. Chem. Soc. 2006, 128, 2920
II. Chiral Auxiliary Strategies
OBO
H
R
N
Me
Bu
Bu
O
O H
2,3-Syn Aldols
Evans OxazolidinoneBoron Enolates
Gage, J. R.; Evans, D. A.Org. Synth. 1990, 68, 83
Review"Asymmetric Aldol Reactions Using Boron Enolates"Cowden, C. J.; Paterson, I. Organic Reactions 1997, 51, 1
2,3-Anti Aldols
D. A. Evans et al.J. Am. Chem. Soc. 2002 124, 392
and Org. Lett. 2002, 4, 1127
(1) Evans Dones
(2) Oppolzer Sultams
NS
OO OSiR3
H
R
OH
Me
L.A.
(3) Masamune Esters
Review"Boron-Mediated Aldol Reaction of Carboxylic Esters"Abiko, A. Acc. Chem. Res. 2004, 37, 387see also Org. Synth. 2002, 79, 109 and 116