Synthesis of 2,6-disubstituted piperidine alkaloids from ladybird beetles Calvia 10-guttata and Calvia 14-guttata

被引：22

作者：

Kubizna, Peter ^{[1
]}

Spanik, Ivan ^{[2
]}

Kozisek, Jozef ^{[3
]}

Szolcsanyi, Peter ^{[1
]}

机构：

[1] Slovak Univ Technol Bratislava, Dept Organ Chem, SK-81237 Bratislava, Slovakia

[2] Slovak Univ Technol Bratislava, Dept Analyt Chem, SK-81237 Bratislava, Slovakia

[3] Slovak Univ Technol Bratislava, Dept Phys Chem, SK-81237 Bratislava, Slovakia

来源：

TETRAHEDRON | 2010年 / 66卷 / 13期

关键词：

Palladium; Carbonylation; Amino alcohols; Heterogeneous catalysis; Natural products; POTENTIAL GLYCOSIDASE INHIBITORS; O-CENTERED NUCLEOPHILES; DOUBLE-BOND GEOMETRY; INTRAMOLECULAR AMINOCARBONYLATION; TETHERED ACRYLATES; TERMINAL EPOXIDES; MICHAEL ADDITION; RESIN GLYCOSIDES; METAL CATALYSIS; C-6; HOMOLOGS;

D O I：

10.1016/j.tet.2010.01.106

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Optically pure (+)-calvine, (+)-2-epicalvine, (2S,6S)-(6-pentylpiperidin-2-yl)acetic acid methyl ester and (2R,6S)-(6-pentylpiperidin-2-yl)acetic acid methyl ester, four piperidine alkaloids isolated from ladybird beetles of the genus Calvia (Coccinellidae), were synthesised from a common precursor using cyclisative Pd(II)/Cu(II)-catalysed carboamination-(methoxy)carbonylation tandem reaction of alkenylamines as a key step. The first single-crystal X-ray analysis of (+)-calvine confirmed its proposed absolute configuration to be (2S,6S) corresponding to that of natural product. (C) 2010 Elsevier Ltd. All rights reserved.

引用

页码：2351 / 2355

页数：5

共 44 条

[1] NITRONE CYCLOADDITION-BASED ENTRY TO THE COCCINELLINE ALKALOID SKELETON - SYNTHESIS OF (+/-)-EPI-HIPPODAMINE [J].

ADAMS, DR ;

CARRUTHERS, W ;

CROWLEY, PJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (18) :1261-1263

[2] Intramolecular Michael addition of N- and O-centred nucleophiles to tethered acrylates. The role of double-bond geometry in controlling the diastereoselectivity of cyclizations leading to 2,6-disubstituted tetrahydropyrans and piperidines [J].

Banwell, MG ;

Bissett, BD ;

Bui, CT ;

Pham, HTT ;

Simpson, GW .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1998, 51 (01) :9-18

[3] Michael addition of N- and O-centred nucleophiles to tethered acrylates. The role of double bond geometry in controlling the diastereoselectivity of cyclisations leading to 2,6-disubstituted tetrahydropyrans and piperidines [J].

Banwell, MG ;

Bui, CT ;

Pham, HTT ;

Simpson, GW .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1996, (10) :967-969

[4] Facile synthesis of α,α′ disubstituted N-hydroxypyrrolidines and N-hydroxypiperidines via double 1,4-addition of hydroxylamine [J].

Bargiggia, FC ;

Murray, WV .

TETRAHEDRON LETTERS, 2006, 47 (19) :3191-3193

[5]

Braekman JC, 1999, EUR J ORG CHEM, V1999, P1749

[6] Stereocontrolled reduction of chiral pyrrolidine and piperidine β-enamino esters:: formal enantioselective synthesis of (+)-calvine [J].

Calvet-Vitale, S ;

Vanucci-Bacqué, C ;

Fargeau-Bellassoued, MC ;

Lhommet, G .

TETRAHEDRON, 2005, 61 (32) :7774-7782

[7]

CHATTOPADHYAY S, 1990, B SOC CHIM FR, P108

[8] Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones:: routes to (-)-(R)- and (+)-(S)-10-methyldodecyl acetate, (-)-(R)-10-methyl-2-tridecanone, (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (-)-(1R,7R)-1,7-dimethylnonyl propanoate, (-)-(6R,12R)-6,12-dimethylpentadecan-2-one, (-)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane [J].

Chow, S ;

Kitching, W .

TETRAHEDRON-ASYMMETRY, 2002, 13 (07) :779-793

[9]

CSATAYOVA K, 2009, THESIS SLOVAK U TECH

[10]

Daloze Desire, 1995, Chemoecology, V5-6, P173, DOI 10.1007/BF01240602

← 1 2 3 4 5 →