Organocatalysis - Organocatalysis lost: Modern chemistry, ancient chemistry, and an unseen biosynthetic apparatus

被引:457
作者
Barbas, Carlos F., III [1 ,2 ,3 ]
机构
[1] Scripps Res Inst, Skaggs Inst Chem Biol, La Jolla, CA 92037 USA
[2] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA
[3] Scripps Res Inst, Dept Mol Biol, La Jolla, CA 92037 USA
关键词
aldolases; asymmetric synthesis; biosynthesis; catalytic antibodies; organocatalysis;
D O I
10.1002/anie.200702210
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(Figure Presented) One enigma leads in three directions: The Hajos-Wiechert reaction presented an enigma that went unsolved for three decades. With the unravelling of this enigma, organocatalysis plays a major role in the development of efficient catalytic asymmetric methodologies. The mechanisms of organocatalysis also shed light on the origin of homochirality essential for life and provide clues to yet-to-be-discovered biosynthetic mechanisms at work in living organisms today. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
引用
收藏
页码:42 / 47
页数:6
相关论文
共 102 条
[1]   KINETIC-ANALYSIS OF THE DUAL CATALYSIS BY PROLINE IN THE ASYMMETRIC INTRAMOLECULAR ALDOL REACTION [J].
AGAMI, C ;
PUCHOT, C .
JOURNAL OF MOLECULAR CATALYSIS, 1986, 38 (03) :341-343
[2]   IS THE MECHANISM OF THE PROLINE-CATALYZED ENANTIOSELECTIVE ALDOL REACTION RELATED TO BIOCHEMICAL PROCESSES [J].
AGAMI, C ;
PUCHOT, C ;
SEVESTRE, H .
TETRAHEDRON LETTERS, 1986, 27 (13) :1501-1504
[3]   A NEW DIAGNOSTIC-TOOL FOR ELUCIDATING THE MECHANISM OF ENANTIOSELECTIVE REACTIONS - APPLICATION TO THE HAJOS-PARRISH REACTION [J].
AGAMI, C ;
LEVISALLES, J ;
PUCHOT, C .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (08) :441-442
[4]   STEREOCHEMISTRY .59. NEW INSIGHTS INTO THE MECHANISM OF THE PROLINE-CATALYZED ASYMMETRIC ROBINSON CYCLIZATION - STRUCTURE OF 2 INTERMEDIATES - ASYMMETRIC DEHYDRATION [J].
AGAMI, C ;
MEYNIER, F ;
PUCHOT, C ;
GUILHEM, J ;
PASCARD, C .
TETRAHEDRON, 1984, 40 (06) :1031-1038
[5]   New strategies for organic catalysis: The first highly enantioselective organocatalytic Diels-Alder reaction [J].
Ahrendt, KA ;
Borths, CJ ;
MacMillan, DWC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (17) :4243-4244
[6]   Theory of asymmetric organocatalysis of aldol and related reactions: Rationalizations and predictions [J].
Allemann, C ;
Gordillo, R ;
Clemente, FR ;
Cheong, PHY ;
Houk, KN .
ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (08) :558-569
[7]   Quantum mechanical predictions of the stereoselectivities of proline-catalyzed asymmetric intermolecular aldol reactions [J].
Bahmanyar, S ;
Houk, KN ;
Martin, HJ ;
List, B .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (09) :2475-2479
[8]   Origins of opposite absolute stereloselectivities in proline-catalyzed direct Mannich and aldol reactions [J].
Bahmanyar, S ;
Houk, KN .
ORGANIC LETTERS, 2003, 5 (08) :1249-1251
[9]   The origin of stereoselectivity in proline-catalyzed intramolecular aldol reactions [J].
Bahmanyar, S ;
Houk, KN .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (51) :12911-12912
[10]   Immune versus natural selection: Antibody aldolases with enzymic rates but broader scope [J].
Barbas, CF ;
Heine, A ;
Zhong, GF ;
Hoffmann, T ;
Gramatikova, S ;
Bjornestedt, R ;
List, B ;
Anderson, J ;
Stura, EA ;
Wilson, IA ;
Lerner, RA .
SCIENCE, 1997, 278 (5346) :2085-2092