TY - JOUR
T1 - Stereospecific Allylic Functionalization
T2 - The Reactions of Allylboronate Complexes with Electrophiles
AU - García-Ruiz, Cristina
AU - Chen, Jack L.Y.
AU - Sandford, Christopher
AU - Feeney, Kathryn
AU - Lorenzo, Paula
AU - Berionni, Guillaume
AU - Mayr, Herbert
AU - Aggarwal, Varinder K.
N1 - Funding Information:
We thank EPSRC (EP/I038071/1), ERC (670668) and Deutsche Forschungsgemeinschaft (SFB 749, project B1) for financial support. C.G.-R. thanks the Ramoń Areces Foundation and P.L. thanks Xunta de Galicia for postdoctoral fellowships. C.S. thanks the University of Bristol for a Ph.D. scholarship and K.F. thanks the EPSRC Bristol Chemical Synthesis Doctoral Training Centre for a studentship (EP/L015366/1). We thank E. M. Wöllner and P. Gansheimer for initial kinetic results, and A. R. Ofial for helpful discussions.
Publisher Copyright:
© 2017 American Chemical Society.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2017/11/1
Y1 - 2017/11/1
N2 - Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser's salt, Togni's reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. The allylboronate complexes were determined to be 7 to 10 orders of magnitude more reactive than the parent boronic ester.
AB - Allylboronic esters react readily with carbonyls and imines (π-electrophiles), but are unreactive toward a range of other electrophiles. By addition of an aryllithium, the corresponding allylboronate complexes display enhanced nucleophilicity, enabling addition to a range of electrophiles (tropylium, benzodithiolylium, activated pyridines, Eschenmoser's salt, Togni's reagent, Selectfluor, diisopropyl azodicarboxylate (DIAD), MeSX) in high regio- and stereocontrol. This protocol provides access to key new functionalities, including quaternary stereogenic centers bearing moieties such as fluorine and the trifluoromethyl group. The allylboronate complexes were determined to be 7 to 10 orders of magnitude more reactive than the parent boronic ester.
UR - http://www.scopus.com/inward/record.url?scp=85032626659&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b10240
DO - 10.1021/jacs.7b10240
M3 - Article
AN - SCOPUS:85032626659
SN - 0002-7863
VL - 139
SP - 15324
EP - 15327
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 43
ER -