The rearrangement of 2,3-epoxysulfonates and its application to natural products syntheses:: Formal synthesis of (-)-aphanorphine and total syntheses of (-)-α-herbertenol and (-)-herbertenediol

被引：73

作者：

Kita, Y ^{[1
]}

Futamura, J ^{[1
]}

Ohba, Y ^{[1
]}

Sawama, Y ^{[1
]}

Ganesh, JK ^{[1
]}

Fujioka, H ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Pharmaceut Sci, Suita, Osaka 5650871, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 15期

关键词：

D O I：

10.1021/jo034573g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The Lewis acid treatment of 2,3-epoxysulfonates with 2,3-dialkyl substituents or 2-alkyl-3-aryl substituents produced the rearrangement products via C3-cleavage of the oxirane ring in high yields. On the other hand, 2-aryl-3-alkyl-2,3-epoxysulfonates produced the products via C2-cleavage of the oxirane ring. The sulfonyloxy groups of the alpha-sulfonyloxy ketones, having a chiral benzylic quaternary carbon center obtained by the rearrangement of 2-alkyl-3-aryl-2,3-epoxysulfonates, were reductively eliminated to give the ketones with a chiral benzylic quaternary carbon center. The method was applied to the formal synthesis of (-)-aphanorphine and total syntheses of (-)-alpha-herbertenol and (-)-herbertenediol.

引用

页码：5917 / 5924

页数：8

共 48 条

[1] New route to herbertanes via a Suzuki cross-coupling reaction:: synthesis of herbertenediol [J].

Abad, A ;

Agulló, C ;

Cuñat, AC ;

Jiménez, D ;

Perni, RH .

TETRAHEDRON, 2001, 57 (48) :9727-9735

[2]

ADAD A, 1999, J ORG CHEM, V64, P1741

[3] Nondynamic and dynamic kinetic resolution of lactones with stereogenic centers and axes: Stereoselective total synthesis of herbertenediol and mastigophorenes A and B [J].

Bringmann, G ;

Pabst, T ;

Henschel, P ;

Kraus, J ;

Peters, K ;

Peters, EM ;

Rycroft, DS ;

Connolly, JD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (38) :9127-9133

[4] Novel concepts in directed biaryl synthesis - Part 76 - First synthesis of mastigophorenes A and B, by biomimetic oxidative coupling of herbertenediol [J].

Bringmann, G ;

Pabst, T ;

Rycroft, DS ;

Connolly, JD .

TETRAHEDRON LETTERS, 1999, 40 (03) :483-486

[5] THERMAL REACTIONS OF ALKYL N-CARBOMETHOXYSULFAMATE ESTERS [J].

BURGESS, EM ;

PENTON, HR ;

TAYLOR, EA .

JOURNAL OF ORGANIC CHEMISTRY, 1973, 38 (01) :26-31

[6]

CHAU P, 1987, P NATL SCI COUNC R A, V43, P124

[7] A STABLE AND EASILY PREPARED CATALYST FOR THE ENANTIOSELECTIVE REDUCTION OF KETONES - APPLICATIONS TO MULTISTEP SYNTHESES [J].

COREY, EJ ;

BAKSHI, RK ;

SHIBATA, S ;

CHEN, CP ;

SINGH, VK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (25) :7925-7926

[8]

CRISAN C, 1957, B SOC CHIM FR, P1451

[9] Total syntheses of (-)-herbertenediol, (-)-mastigophorene A, and (-)-mastigophorene B. Combined utility of chiral bicyclic lactams and chiral aryl oxazolines [J].

Degnan, AP ;

Meyers, AI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (12) :2762-2769

[10] Enzymatic asymmetrisation of prochiral alpha,alpha-disubstituted-malonates and -1,3-propanediols: Formal asymmetric syntheses of (-)-aphanorphine and (+)-eptazocine [J].

Fadel, A ;

Arzel, P .

TETRAHEDRON-ASYMMETRY, 1997, 8 (03) :371-374

← 1 2 3 4 5 →