Site‐Selective (Z)‐α‐Borylalkenyl Copper Systems for Nucleophilic Stereodefined Allylic Coupling

1,1‐Diborylalkenes can be transformed into (Z)‐skipped dienes through CuI‐phosphine catalyzed allylic coupling reactions. The energetically preferred formation of (Z)‐α‐borylalkenyl copper (I) species and the subsequent nucleophilic attack, explains the stereoselective nucleophilic substitution with...

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Published inAngewandte Chemie Vol. 134; no. 37
Main Authors Pujol, Mireia, Maza, Ricardo J., Salvado, Oriol, Carbó, Jorge J., Fernández, Elena
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 12.09.2022
Subjects
1,1-Diborylalkenes
Allylic Coupling
Bromides
Chemical reactions
Chemistry
Copper
Coupling
Dienes
Intermediates
Phosphine
Phosphines
Skipped Dienes
Stereoselective Synthesis
Stereoselectivity
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Summary:1,1‐Diborylalkenes can be transformed into (Z)‐skipped dienes through CuI‐phosphine catalyzed allylic coupling reactions. The energetically preferred formation of (Z)‐α‐borylalkenyl copper (I) species and the subsequent nucleophilic attack, explains the stereoselective nucleophilic substitution with allyl bromides. The eventual treatment of (Z)‐skipped dienes with NaOtBu promotes cyclization/aromatization patterns via enyne intermediates. A CuI‐phosphine catalytic system activates 1,1‐diborylalkenes stereoselectively. The energetically preferred formation of (Z)‐α‐borylalkenyl copper(I) species and the subsequent coupling reaction with allyl bromides allow the exclusive formation of (Z)‐skipped dienes. This new methodology is applicable to various 1,1‐di(pinacolboryl)alkenes which can be efficiently coupled with different types of allyl halides. The (Z)‐skipped dienes with bromide functionality are treated with NaOtBu to promote cyclization/aromatization patterns via enyne intermediates.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202208495