TY - JOUR
T1 - Stereospecific ring contraction of bromocycloheptenes through dyotropic rearrangements via nonclassical carbocation-anion pairs
AU - Goh, Shermin S.
AU - Champagne, Pier Alexandre
AU - Guduguntla, Sureshbabu
AU - Kikuchi, Takashi
AU - Fujita, Makoto
AU - Houk, K. N.
AU - Feringa, Ben L.
N1 - Funding Information:
B.L.F. acknowledges The Netherlands Organization for Scientific Research (NWO-CW), the Royal Netherland Academy of Arts and Sciences (KNAW), and the Ministry of Education Culture and Science (Gravitation program 024.601035) for funding. S.S.G. acknowledges A*STAR (NSS) for a postdoctoral fellowship. P.A.C. acknowledges the FRQNT for a postdoctoral fellowship. We are grateful to the NSF (CHE-1361104 to K.N.H.) for financial support of this research. Computations were performed on the Hoffman2 cluster at UCLA. M.F. and T.K. acknowledge JST-ACCEL project in which M.F. is a principal investigator.
Funding Information:
B.L.F. acknowledges The Netherlands Organization for Scientific Research (NWO-CW), the Royal Netherland Academy of Arts and Sciences (KNAW), and the Ministry of Education Culture and Science (Gravitation program 024.601035) for funding. S.S.G. acknowledges A∗STAR (NSS) for a postdoctoral fellowship. P.A.C. acknowledges the FRQNT for a postdoctoral fellowship. We are grateful to the NSF (CHE-1361104 to K.N.H.) for financial support of this research. Computations were performed on the Hoffman2 cluster at UCLA. M.F. and T.K. acknowledge JST-ACCEL project in which M.F. is a principal investigator.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/4/18
Y1 - 2018/4/18
N2 - Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.
AB - Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.
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U2 - 10.1021/jacs.8b00821
DO - 10.1021/jacs.8b00821
M3 - Article
C2 - 29596748
AN - SCOPUS:85045680257
SN - 0002-7863
VL - 140
SP - 4986
EP - 4990
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 15
ER -