TY - JOUR
T1 - Catalytic Access to Diastereometrically Pure Four- and Five-Membered Silyl-Heterocycles Using Transborylation
AU - Willcox, Dominic R.
AU - Cocco, Emanuele
AU - Nichol, Gary S.
AU - Carlone, Armando
AU - Thomas, Stephen P.
N1 - Publisher Copyright:
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2024/6/3
Y1 - 2024/6/3
N2 - 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.
AB - 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.
KW - Boron
KW - Catalysis
KW - Main group
KW - Silicon
KW - Transborylation
U2 - 10.1002/anie.202401737
DO - 10.1002/anie.202401737
M3 - Article
C2 - 38578174
AN - SCOPUS:85191970572
SN - 1433-7851
VL - 63
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 23
M1 - e202401737
ER -