A MEANS FOR STEREOCONTROLLED INTRODUCTION OF THE C-2 OXYGEN SUBSTITUENT IN FUNCTIONALIZED CIS-TRICYCLO[9.3.1.03,8]PENTADECANONES RELATED TO TAXOL

被引：29

作者：

PAQUETTE, LA

HUBER, SK

THOMPSON, RC

机构：

[1] Evans Chemical Laboratories, The Ohio State University, Columbus

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1993年 / 58卷 / 24期

关键词：

D O I：

10.1021/jo00076a058

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Several optically pure cis-tricyclo[9.3.1.0(3,8)]pentadecanones have been prepared via anionic oxy-Cope rearrangement of exo-norbornanol precursors that have been obtained by convergent coupling of two functionalized reaction partners. The sigmatropic rearrangement is shown to proceed with exceptionally good stereochemical transmission because of universal adherence to the same endo-chair transition state. The atropisomeric aspects of this pivotal transformation are addressed. Also investigated was the proclivity of the products to undergo transannular hemiketal formation following osmylation of the bridgehead double bond. As matters turn out, the operation or nonoperation of this intramolecular addition to the C-9 carbonyl group is amenable to control merely by adjusting properly the stereochemistry of a single pendant substituent.

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页码：6874 / 6882

页数：9

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[11] PI-FACIALLY CONTROLLED NUCLEOPHILIC ADDITIONS OF CHIRAL VINYLORGANOMETALLICS TO CHIRAL BETA,GAMMA-UNSATURATED KETONES .1. DOUBLE DIASTEREOSELECTION STUDIES INVOLVING 7,7-DIMETHOXY-5-NORBORNEN-2-ONE [J].

PAQUETTE, LA ;

LEARN, KS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (24) :7873-7875

[12] TOTAL SYNTHESIS OF (+)-IKARUGAMYCIN .1. STEREOCONTROLLED CONSTRUCTION OF THE DECAHYDRO-ASYM-INDACENE SUBUNIT [J].

PAQUETTE, LA ;

ROMINE, JL ;

LIN, HS ;

WRIGHT, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (25) :9284-9292

[13] DIRECT OXYGENATION OF ENOLATES GENERATED BY ANIONIC OXY-COPE REARRANGEMENT - EXPEDIENT PREPARATION OF POLYCYCLIC ALPHA-HYDROXY KETONES [J].

PAQUETTE, LA ;

DERUSSY, DT ;

PEGG, NA ;

TAYLOR, RT ;

ZYDOWSKY, TM .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (19) :4576-4581

[14] SETTING THE BRIDGEHEAD OXIDATION LEVEL IN TRANS-TRICYCLO[9.3.1.0(3),8]PENTADECANES AS A PRELUDE TO THE DUAL SYNTHESIS OF TAXOL AND TAXUSIN [J].

PAQUETTE, LA ;

COMBRINK, KD ;

ELMORE, SW ;

ZHAO, M .

HELVETICA CHIMICA ACTA, 1992, 75 (06) :1772-1791

[15] MOLECULAR RECOGNITION DURING 1,2-ADDITION OF CHIRAL VINYL ORGANOMETALLICS TO CHIRAL-BETA,GAMMA-UNSATURATED KETONES - CASE STUDIES OF 3 7,7-DISUBSTITUTED 2-NORBORNENONES .5. [J].

PAQUETTE, LA ;

LEARN, KS ;

ROMINE, JL ;

LIN, HS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (03) :879-890

[16] [3.3] SIGMATROPY WITHIN 1-VINYL-2-ALKENYL-7,7-DIMETHYL-EXO-NORBORNAN-2-OLS - THE 1ST ATROPSELECTIVE OXYANIONIC COPE REARRANGEMENT [J].

PAQUETTE, LA ;

PEGG, NA ;

TOOPS, D ;

MAYNARD, GD ;

ROGERS, RD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (01) :277-283

[17] AN ENANTIOSELECTIVE APPROACH TO THE TAXANES - DIRECT ACCESS TO FUNCTIONALIZED CIS-TRICYCLO[9.3.1.0(3,8)]PENTADECANES VIA ALPHA-HYDROXY KETONE AND WAGNER-MEERWEIN REARRANGEMENTS [J].

PAQUETTE, LA ;

ELMORE, SW ;

COMBRINK, KD ;

HICKEY, ER ;

ROGERS, RD .

HELVETICA CHIMICA ACTA, 1992, 75 (06) :1755-1771

[18] IMPACT OF SUBSTITUENT MODIFICATIONS ON THE ATROPSELECTIVITY CHARACTERISTICS OF AN ANIONIC OXY-COPE RING EXPANSION [J].

PAQUETTE, LA ;

COMBRINK, KD ;

ELMORE, SW ;

ROGERS, RD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (04) :1335-1344

[19] FUNCTIONALIZATION REACTIONS OF A MEDIUM-RING BRIDGEHEAD ENONE THAT SKIRT TRANSANNULAR BOND FORMATION [J].

PEGG, NA ;

PAQUETTE, LA .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (07) :2461-2468

[20] SYNTHESIS AND CIRCULAR-DICHROISM OF SOME BICYCLIC COMPOUNDS RELATED TO CAMPHOR WITH CHIRALITY DUE TO DEUTERIUM SUBSTITUTION [J].

POLONSKI, T .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1983, (02) :305-309