Enantioselective synthesis and absolute configurations of aculeatins A, B, D, and 6-epi-aculeatin D

被引:42
作者
Alvarez-Bercedo, Paula
Falomir, Eva [1 ]
Carda, Miguel
Marco, J. A.
机构
[1] Univ Jaume 1, Depart Q Inorgan & Organ, E-12080 Castellon de La Plana, Spain
[2] Univ Valencia, Depart Q Organ, E-46100 Burjassot, Valencia, Spain
关键词
aculeatins; absolute configuration; asymmetric allylation; aldol reaction; remote induction; spiroacetals; hypervalent iodine; oxidative spiroacetalization;
D O I
10.1016/j.tet.2006.07.076
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The three naturally occurring, bioactive spiroacetals aculeatins A, B, and D, as well as the non-natural 6-epi-aculeatin D have been synthesized for the first time in enantiopure form using an asymmetric allylation as the only chirality source. A further key step was a stereo-selective aldol reaction with remote induction. The absolute configurations of the natural products have been established and an erroneous structural assignment has been corrected. (c) 2006 Elsevier Ltd. All rights reserved.
引用
收藏
页码:9641 / 9649
页数:9
相关论文
共 40 条
[1]  
[Anonymous], 1997, ORG REACT
[2]   Biomimetic synthesis of (±)-aculeatin D [J].
Baldwin, JE ;
Adlington, RM ;
Sham, VWW ;
Marquez, R ;
Bulger, PG .
TETRAHEDRON, 2005, 61 (09) :2353-2363
[3]   Synthesis of bis-spiroacetal ring systems [J].
Brimble, MA ;
Farès, FA .
TETRAHEDRON, 1999, 55 (25) :7661-7706
[4]   Fundamental role of the fostriecin unsaturated lactone and implications for selective protein phosphatase inhibition [J].
Buck, SB ;
Hardouin, C ;
Ichikawa, S ;
Soenen, DR ;
Gauss, CM ;
Hwang, I ;
Swingle, MR ;
Bonness, KM ;
Honkanen, RE ;
Boger, DL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (51) :15694-15695
[5]   Efficient oxidative spirocyclization of phenolic sulfonamides [J].
Canesi, S ;
Belmont, P ;
Bouchu, D ;
Rousset, L ;
Ciufolini, MA .
TETRAHEDRON LETTERS, 2002, 43 (29) :5193-5195
[6]   DIRECTED REDUCTION OF BETA-HYDROXY KETONES EMPLOYING TETRAMETHYLAMMONIUM TRIACETOXYBOROHYDRIDE [J].
EVANS, DA ;
CHAPMAN, KT ;
CARREIRA, EM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (11) :3560-3578
[7]   1,5-asymmetric induction in boron-mediated β-alkoxy methyl ketone aldol addition reactions [J].
Evans, DA ;
Côté, B ;
Coleman, PJ ;
Connell, BT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (36) :10893-10898
[8]   Enantioselective synthesis and absolute configurations of aculeatins A and B [J].
Falomir, E ;
Alvarez-Bercedo, P ;
Carda, M ;
Marco, JA .
TETRAHEDRON LETTERS, 2005, 46 (48) :8407-8410
[9]   ANOMERIC EFFECT - ORIGIN AND CONSEQUENCES [J].
GRACZYK, PP ;
MIKOLAJCZYK, M .
TOPICS IN STEREOCHEMISTRY, VOL 21, 1994, 21 :159-349
[10]  
Heilmann J, 2000, HELV CHIM ACTA, V83, P2939, DOI 10.1002/1522-2675(20001108)83:11&lt