Dual catalyst control in the enantioselective intramolecular Morita-Baylis-Hillman reaction

被引：109

作者：

Aroyan, CE ^{[1
]}

Vasbinder, MM ^{[1
]}

Miller, SJ ^{[1
]}

机构：

[1] Boston Coll, Merkert Chem Ctr, Dept Chem, Chestnut Hill, MA 02467 USA

来源：

ORGANIC LETTERS | 2005年 / 7卷 / 18期

关键词：

D O I：

10.1021/ol0513544

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The intramolecular Morita-Baylis-Hillman (MBH) reaction has been achieved with unprecedented levels of enantioselectivity. Using a cocatalyst system involving pipecolinic acid and N-methylimidazole, cyclic MBH products have been obtained with enantiomer ratios of 92:8 (84% ee). In addition, reactions may be carried out with a "kinetic resolution quench" involving acetic anhydride and an asymmetric acylation catalyst such that ee enhancement occurs to deliver products with > 98% ee with an isolated yield of 50%.

引用

页码：3849 / 3851

页数：3

共 30 条

[1] Reevaluation of the mechanism of the Baylis-Hillman reaction: Implications for asymmetric catalysis
Aggarwal, VK
Fulford, SY
Lloyd-Jones, GC
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (11) : 1706 - 1708
[2] Asymmetric Baylis-Hillman reactions: catalysis using a chiral pyrrolizidine base
Barrett, AGM
Cook, AS
Kamimura, A
[J]. CHEMICAL COMMUNICATIONS, 1998, (22) : 2533 - 2534
[3] Recent advances in the Baylis-Hillman reaction and applications
Basavaiah, D
Rao, AJ
Satyanarayana, T
[J]. CHEMICAL REVIEWS, 2003, 103 (03) : 811 - 891
[4] Tandem Michael/Michael reactions mediated by phosphines or aryl thiolates
Brown, PM
Käppel, N
Murphy, PJ
[J]. TETRAHEDRON LETTERS, 2002, 43 (48) : 8707 - 8710
[5] Selection of enantioselective acyl transfer catalysts from a pooled peptide library through a fluorescence-based activity assay: An approach to kinetic resolution of secondary alcohols of broad structural scope
Copeland, GT
Miller, SJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (27) : 6496 - 6502
[6] INTRAMOLECULAR BAYLIS-HILLMAN REACTION - A PATHWAY TO SUBSTITUTED COUMARINS
DREWES, SE
NJAMELA, OL
EMSLIE, ND
RAMESAR, N
FIELD, JS
[J]. SYNTHETIC COMMUNICATIONS, 1993, 23 (20) : 2807 - 2815
[7] Structure-selectivity relationships and structure for a peptide-based enantioselective acylation catalyst
Fierman, MB
O'Leary, DJ
Steinmetz, WE
Miller, SJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (22) : 6967 - 6971
[8] The vinylogous intramolecular Morita-Baylis-Hillman reaction: Synthesis of functionalized cyclopentenes and cyclohexenes with trialkylphosphines as nucleophilic catalysts
Frank, SA
Mergott, DJ
Roush, WR
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (11) : 2404 - 2405
[9] Dual catalyst control in the amino acid-peptide-catalyzed enantioselective Baylis-Hillman reaction
Imbriglio, JE
Vasbinder, MM
Miller, SJ
[J]. ORGANIC LETTERS, 2003, 5 (20) : 3741 - 3743
[10] Chiral amine-catalyzed asymmetric Baylis-Hillman reaction:: A reliable route to highly enantiomerically enriched (α-methylene-β-hydroxy)esters
Iwabuchi, Y
Nakatani, M
Yokoyama, N
Hatakeyama, S
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (43) : 10219 - 10220

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