ASYMMETRIC-SYNTHESIS OF THE KEY INTERMEDIATES LEADING TO (-)-APHANORPHINE AND (-)-EPTAZOCINE

被引：74

作者：

HULME, AN ^{[1
]}

HENRY, SS ^{[1
]}

MEYERS, AI ^{[1
]}

机构：

[1] COLORADO STATE UNIV,DEPT CHEM,FT COLLINS,CO 80523

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 05期

关键词：

D O I：

10.1021/jo00110a033

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The asymmetric syntheses of two key intermediates, 8 and 15, in >99% ee are reported. These compounds are prepared by diastereofacial addition of lithiodimethylphenylsilane to chiral naphthyloxazolines followed by methyl iodide trapping. The two stereocenters are formed in greater than 95% ds, and the silyl center is subsequently removed to give the 1,1-disubstituted tetralins 8, 9, or 12. These chiral substances are readily transformed into the titled compounds as described in the literature. The absolute configuration of these intermediates has been confirmed by X-ray analysis and corrects an earlier misassignment.

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页码：1265 / 1270

页数：6

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共 24 条

[1] A NOVEL STEREOSELECTIVE AND ENANTIOSELECTIVE SYNTHESIS OF TRANS-9-ALKYL-2-BENZYL-5-METHYL-6,7-BENZOMORPHANS [J].

DEHGHANI, A ;

BAI, X ;

MASCARELLA, SW ;

BOWEN, WD ;

CARROLL, FI .

TETRAHEDRON LETTERS, 1994, 35 (48) :8969-8972

[2] RHODIUM(I)-CATALYZED HYDROBORATION OF OLEFINS - THE DOCUMENTATION OF REGIOCHEMICAL AND STEREOCHEMICAL CONTROL IN CYCLIC AND ACYCLIC SYSTEMS [J].

EVANS, DA ;

FU, GC ;

HOVEYDA, AH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (20) :6917-6918

[3] THE SILYLCUPRATION OF ACETYLENES - A SYNTHESIS OF VINYLSILANES [J].

FLEMING, I ;

NEWTON, TW ;

ROESSLER, F .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1981, (09) :2527-2532

[4] 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

[5] ASYMMETRIC-SYNTHESIS OF 1,1-DISUBSTITUTED TETRALINS AND DIHYDRONAPHTHALENES BY DIASTEREOSELECTIVE ADDITION OF LITHIOSILANES TO CHIRAL NAPHTHALENES [J].

HULME, AN ;

MEYERS, AI .

JOURNAL OF ORGANIC CHEMISTRY, 1994, 59 (05) :952-953

[6] STUDIES IN DEHYDROGENATION OF 6-METHOXY-1-TETRALONE . STRUCTURE OF A NOVEL PRODUCT FORMED WITH TETRACHLORO-1,2-BENZOQUINONE [J].

KASTURI, TR ;

ARUNACHA.T .

CANADIAN JOURNAL OF CHEMISTRY, 1968, 46 (23) :3625-&

[7]

KONDO K, 1993, SYNTHESIS-STUTTGART, P920

[8] THE WITTIG OLEFINATION REACTION AND MODIFICATIONS INVOLVING PHOSPHORYL-STABILIZED CARBANIONS - STEREOCHEMISTRY, MECHANISM, AND SELECTED SYNTHETIC ASPECTS [J].

MARYANOFF, BE ;

REITZ, AB .

CHEMICAL REVIEWS, 1989, 89 (04) :863-927

[9] ASYMMETRIC-SYNTHESIS OF 2-ALKYLPYRROLIDINES AND PIPERIDINES - SYNTHESIS OF (+)-METAZOCINE [J].

MEYERS, AI ;

DICKMAN, DA ;

BAILEY, TR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (26) :7974-7978

[10] AN ASYMMETRIC-SYNTHESIS OF (+)-MORPHINANS IN HIGH ENANTIOMERIC PURITY [J].

MEYERS, AI ;

BAILEY, TR .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (06) :872-875