On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides

Scott E. Denmark; Nathan S. Werner

doi:10.1021/ja910804u

On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides

Scott E. Denmark, Nathan S. Werner

Chemistry

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Abstract

The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, a-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a coppercatalyzed S_N2′ reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent crosscoupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn S_E′ mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.

Original language	English (US)
Pages (from-to)	3612-3620
Number of pages	9
Journal	Journal of the American Chemical Society
Volume	132
Issue number	10
DOIs	https://doi.org/10.1021/ja910804u
State	Published - Mar 17 2010

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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abstract = "The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, a-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a coppercatalyzed SN2′ reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent crosscoupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn SE′ mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.",

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AB - The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, a-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a coppercatalyzed SN2′ reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent crosscoupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn SE′ mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.

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On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides

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