Enantioselective Formal [4+1] Cycloaddition of Diazoarylacetates and the Danishefsky’s Diene: Stereoselective Synthesis of (−)-1,13-Herbertenediol

Fang Hu; Qing Zhou; Fei Cao; Wen-Dao Chu; Long He; Quan-Zhong Liu

doi:10.1021/acs.joc.8b01546

Enantioselective Formal [4+1] Cycloaddition of Diazoarylacetates and the Danishefsky’s Diene: Stereoselective Synthesis of (−)-1,13-Herbertenediol

The Journal of Organic Chemistry ◽

10.1021/acs.joc.8b01546 ◽

2018 ◽

Vol 83 (20) ◽

pp. 12806-12814 ◽

Cited By ~ 3

Author(s):

Fang Hu ◽

Qing Zhou ◽

Fei Cao ◽

Wen-Dao Chu ◽

Long He ◽

...

Keyword(s):

Stereoselective Synthesis ◽

Danishefsky's Diene

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Stereoselective synthesis of chiral piperidine derivatives employing arabinopyranosylamine as the carbohydrate auxiliary

Canadian Journal of Chemistry ◽

10.1139/v06-060 ◽

2006 ◽

Vol 84 (4) ◽

pp. 625-641 ◽

Cited By ~ 16

Author(s):

Birgit Kranke ◽

Horst Kunz

Keyword(s):

Structure Analysis ◽

Absolute Configuration ◽

Electrophilic Substitution ◽

Stereoselective Synthesis ◽

Michael Reaction ◽

Coupling Reactions ◽

X Ray ◽

Enolate Alkylation ◽

Palladium Catalyzed ◽

Danishefsky's Diene

Stereoselective synthesis of 2-substituted dehydropiperidinones and their further transformation to variously disubstituted piperidine derivatives was achieved employing D-arabinopyranosylamine as the stereodifferentiating carbohydrate auxiliary. A domino MannichMichael reaction of 1-methoxy-3-(trimethylsiloxy)butadiene (Danishefsky's diene) with O-pivaloylated arbinosylaldimines furnished N-arabinosyl dehydropiperidinones in high diastereoselectivity. Subsequent conjugate cuprate addition gave 2,6-cis-substituted piperidinones, while enolate alkylation furnished 2,3-trans-substituted dehydropiperidinones. Electrophilic substitution at the enamine structure afforded 5-nitro- and 5-halogen dehydropiperidinones of which the latter were applied in palladium-catalyzed coupling reactions. The absolute configuration of the obtained products was proven by NMR and X-ray structure analysis as well as by syntheses of the alkaloids (+)-coniine and (+)-dihydropinidine.Key words: piperidine alkaloids, carbohydrate auxiliary, domino MannichMichael reaction, conjugate cuprate and hydride addition, electrophilic substitution of enamines.

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