Catalytic Access to Diastereometrically Pure Four‐ and Five‐Membered Silyl‐Heterocycles Using Transborylation

Silyl‐heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. The shortage of catalytic methods for the preparation of diverse and functionalized silyl‐heterocycles however limits widespread exploration and exploitation. Herein the borane‐catalyzed int...

Full description

Saved in:
Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 63; no. 23; pp. e202401737 - n/a
Main Authors Willcox, Dominic R., Cocco, Emanuele, Nichol, Gary S., Carlone, Armando, Thomas, Stephen P.
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 03.06.2024
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Alkynes
Boranes
Boron
Catalysis
Catalysts
Chemistry
Chemistry, Multidisciplinary
Esters
Hydroboration
Labeling
Main group
Physical Sciences
Science & Technology
Silicon
Transborylation
HYDROBORATION
CARBON
ANALOGS
CRYSTAL-STRUCTURE
ALKYNYL GROUPS
MAIN-GROUP ELEMENTS
LIGHT-EMITTING-DIODES
Main group
Boron
Transborylation
1,1-ORGANOBORATION
Silicon
Catalysis
BOND
Online AccessGet full text

Cover

More Information
Summary:Silyl‐heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. The shortage of catalytic methods for the preparation of diverse and functionalized silyl‐heterocycles however limits widespread exploration and exploitation. Herein the borane‐catalyzed intramolecular 1,1‐carboboration of silyl‐alkynes has been developed for the synthesis of 2,3‐dihydrosilolyl and silylcyclobut‐2‐enyl boronic esters. Successful, catalytic carboboration has been achieved on a variety of functionally diverse silyl‐alkynes, using a borane catalyst and transborylation‐enabled turnover. Mechanistic studies, including 13C‐labelling, computational studies, and single‐turnover experiments, suggest a reaction pathway proceeding by 1,2‐hydroboration, 1,1‐carboboration, and transborylation to release the alkenyl boronic ester product and regenerate the borane catalyst. Silyl‐heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. These are limited by the lack of catalytic methods for the preparation of diverse and functionalized silyl‐heterocycles. Herein the borane‐catalyzed intramolecular 1,1‐carboboration of silyl‐alkynes has been developed for the synthesis of 2,3‐dihydrosilolyl and silylcyclobut‐2‐enyl boronic esters.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202401737