Total synthesis of (+)-cocaine via desymmetrization of a meso-dialdehyde

被引：54

作者：

Mans, DM ^{[1
]}

Pearson, WH ^{[1
]}

机构：

[1] Univ Michigan, Dept Chem, Ann Arbor, MI 48109 USA

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 19期

关键词：

D O I：

10.1021/ol048777a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The total synthesis of (+)-cocaine is described. An extension of the recently reported proline catalyzed intramolecular enol-exo-aldol reaction to a meso-dialdehyde provided the tropane ring skeleton directly with good enantiomeric excess. The meso-dialdehyde was prepared using a 2-azaallyllithium [3 + 2] cycloaddition to generate a cis-2,5-disubstituted pyrrolidine. Overall, the synthesis proceeded in 6.5% yield and 86% ee over 14 linear steps starting from commercially available 3-benzyloxy-1-propanol.

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页码：3305 / 3308

页数：4

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共 71 条

[1] A concise asymmetric route to the bridged bicyclic tropane alkaloid ferruginine using enyne ring-closing metathesis [J].

Aggarwal, VK ;

Astle, CJ ;

Rogers-Evans, M .

ORGANIC LETTERS, 2004, 6 (09) :1469-1471

[2] A unified asymmetric approach to substituted hexahydroazepine and 7-azabicyclo[2.2.1]heptane ring systems from D(-)-quinic acid: Application to the formal syntheses of (-)-balanol and (-)-epibatidine [J].

Albertini, E ;

Barco, A ;

Benetti, S ;

DeRisi, C ;

Pollini, GP ;

Zanirato, V .

TETRAHEDRON, 1997, 53 (50) :17177-17194

[3] Synthesis of tropinones by Cyclization of 1,3-bis-silyl enol ethers with iminium triflates [J].

Albrecht, U ;

Armbrust, H ;

Langer, P .

SYNLETT, 2004, (01) :143-145

[4] ENANTIOSELECTIVE SYNTHESIS OF THE CARBAPENEM RING-SYSTEM FROM (S)-PROLINE [J].

ASADA, S ;

KATO, M ;

ASAI, K ;

INEYAMA, T ;

NISHI, S ;

IZAWA, K ;

SHONO, T .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (08) :486-488

[5] REDUCTION OF 2,5-DIALKYLPYRROLINES - A KEY STEP IN A SYNTHESIS OF NATURAL INSECTICIDES [J].

BACOS, D ;

CELERIER, JP ;

MARX, E ;

SALIOU, C ;

LHOMMET, G .

TETRAHEDRON LETTERS, 1989, 30 (09) :1081-1082

[6] 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

[7] Transition states of amine-catalyzed aldol reactions involving enamine intermediates: Theoretical studies of mechanism, reactivity, and stereoselectivity [J].

Bahmanyar, S ;

Houk, KN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (45) :11273-11283

[8]

Bahmanyar S., 2001, J AM CHEM SOC, V123, P9922

[9] A short and efficient synthesis of (+)-calystegine B2 [J].

Boyer, FD ;

Hanna, I .

TETRAHEDRON LETTERS, 2001, 42 (07) :1275-1277

[10] ENANTIOSELECTIVE SYNTHESES OF POLYHYDROXYLATED NORTROPANE DERIVATIVES - TOTAL SYNTHESIS OF (+)-CALYSTEGINE-B-2 AND (-)-CALYSTEGINE B-2 [J].

BOYER, FD ;

LALLEMAND, JY .

TETRAHEDRON, 1994, 50 (35) :10443-10458

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