One-pot organocatalytic domino Michael-aldol and intramolecular SN2 reactions.: Asymmetric synthesis of highly functionalized epoxycyclohexanone derivatives

被引:164
作者
Marigo, M [1 ]
Bertelsen, S [1 ]
Landa, A [1 ]
Jorgensen, KA [1 ]
机构
[1] Aarhus Univ, Ctr Catalysis, Dept Chem, Danish Natl Res Fdn, DK-8000 Aarhus C, Denmark
关键词
D O I
10.1021/ja058490o
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The development of the organocatalytic asymmetric one-pot Michael-Darzens condensation giving highly functionalized complex epoxycyclohexanone derivatives with up to four chiral centers is presented. Depending on the reaction conditions, either the polysubstituted 7-oxa-bicyclo[4.1.0]heptan-2-one ring system or 2-chloro-cyclohex-2-enone derivatives can be formed. For the former class of compounds a high diversity in substitution pattern is demonstrated, and the optically active products are obtained in excellent diastereo- and enantioselectivities. The potential synthetic applications of the products have been demonstrated by performing a series of highly diastereoselective transformations leading to optically active products useful for the life-science industry. Furthermore, mechanistic investigations on the formation of the chiral centers in the optically active epoxycyclohexanone are presented.
引用
收藏
页码:5475 / 5479
页数:5
相关论文
共 46 条
[11]   Photochemical rearrangement of 2-phenylthio-1,3-cyclohexanediols to deoxysugars.: Application to a stereospecific synthesis of (+)-cis-rose oxide [J].
Gravel, D ;
Bordeleau, J .
TETRAHEDRON LETTERS, 1998, 39 (44) :8035-8038
[12]   Catalytic asymmetric tandem transformations triggered by conjugate additions [J].
Guo, HC ;
Ma, JA .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (03) :354-366
[13]   ASYMMETRIC SYNTHESIS OF BICYCLIC INTERMEDIATES OF NATURAL PRODUCT CHEMISTRY [J].
HAJOS, ZG ;
PARRISH, DR .
JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (12) :1615-1621
[14]   Highly enantio- and diastereoselective organocatalytic asymmetric domino Michael-Aldol reaction of β-ketoesters and α,β-unsaturated ketones [J].
Halland, N ;
Aburel, PS ;
Jorgensen, KA .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (10) :1272-1277
[15]   A-ring hydroxymethyl 19-nor analogs of the natural hormone 1α,25-dihydroxyvitamin D3:: synthesis and preliminary biological evaluation [J].
Hatcher, MA ;
Peleg, S ;
Dolan, P ;
Kensler, TW ;
Sarjeant, A ;
Posner, GH .
BIOORGANIC & MEDICINAL CHEMISTRY, 2005, 13 (12) :3964-3976
[16]   Diphenylprolinol silyl ethers as efficient organocatalysts for the asymmetric Michael reaction of aldehydes and nitroalkenes [J].
Hayashi, Y ;
Gotoh, H ;
Hayashi, T ;
Shoji, M .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (27) :4212-4215
[17]   Enantioselective organo-cascade catalysis [J].
Huang, Y ;
Walji, AM ;
Larsen, CH ;
MacMillan, DWC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (43) :15051-15053
[18]   Proline-catalyzed asymmetric addition reaction of 9-tosyl-3,4-dihydro-β-carboline with ketones [J].
Itoh, T ;
Yokoya, M ;
Miyauchi, K ;
Nagata, K ;
Ohsawa, A .
ORGANIC LETTERS, 2003, 5 (23) :4301-4304
[19]   The ying and yang of asymmetric aminocatalysis [J].
List, B .
CHEMICAL COMMUNICATIONS, 2006, (08) :819-824
[20]   Enantioselective aldol cyclodehydrations catalyzed by antibody 38C2 [J].
List, B ;
Lerner, RA ;
Barbas, CF .
ORGANIC LETTERS, 1999, 1 (01) :59-61