Synthesis of (-)-aphanorphine using a sulfur-directed aryl radical cyclization

被引：41

作者：

Tamura, O ^{[1
]}

Yanagimachi, T ^{[1
]}

Ishibashi, H ^{[1
]}

机构：

[1] Kanazawa Univ, Fac Pharmaceut Sci, Kanazawa, Ishikawa 9200934, Japan

来源：

TETRAHEDRON-ASYMMETRY | 2003年 / 14卷 / 19期

关键词：

D O I：

10.1016/S0957-4166(03)00530-5

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Treatment of radical precursor 15a having a vinyl sulfide moiety with Bu3SnH in the presence of AIBN in boiling benzene afforded exclusively the 6-exo cyclization product 16a, whereas similar treatment of the exo-methylene compound 15b gave a mixture of the 6-exo cyclization product 16b and the endo-olefin product 17 formed by a 1,5-hydrogen shift. Based on these findings, the synthesis of (-)-aphanorphine was achieved using a sulfur-directed 6-exo-selective aryl radical cyclization of 22. (C) 2003 Elsevier Ltd. All rights reserved.

引用

页码：3033 / 3041

页数：9

共 30 条

[1]

BAIRD MC, 1968, J CHEM SOC, P345

[2]

BARTON DHR, 1984, HETEROCYCLES, V21, P1

[3] Chirospecific syntheses of conformationally constrained 7-azabicycloheptane amino acids by transannular alkylation [J].

Campbell, JA ;

Rapoport, H .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (18) :6313-6325

[4] 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

[5] ASYMMETRIC CONSTRUCTION OF BENZYLIC QUATERNARY CARBONS FROM CHIRAL MALONATES - FORMAL SYNTHESIS OF NATURAL (-)APHANORPHINE [J].

FADEL, A ;

ARZEL, P .

TETRAHEDRON-ASYMMETRY, 1995, 6 (04) :893-900

[6]

François D, 1998, ANGEW CHEM INT EDIT, V37, P104, DOI 10.1002/(SICI)1521-3773(19980202)37:1/2<104::AID-ANIE104>3.0.CO

[7]

2-K

[8] Regioselective aryl radical cyclisation .2. Synthesis of octahydro-1H-dibenzo[a,d]cycloheptenes through 7-endo ring closure [J].

Ghosh, AK ;

Mukhopadhyaya, JK ;

Ghatak, UR .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1997, (18) :2747-2755

[9] ACYL ANION EQUIVALENTS - SYNTHESIS OF KETONES AND ENONES FROM ALPHA-PHENYLTHIOALKYLPHOSPHINE OXIDES [J].

GRAYSON, JI ;

WARREN, S .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1977, (20) :2263-2272

[10] APHANORPHINE, A NOVEL TRICYCLIC ALKALOID FROM THE BLUE-GREEN-ALGA APHANIZOMENON-FLOS-AQUAE [J].

GULAVITA, N ;

HORI, A ;

SHIMIZU, Y ;

LASZLO, P ;

CLARDY, J .

TETRAHEDRON LETTERS, 1988, 29 (35) :4381-4384

← 1 2 3 →