TY - JOUR
T1 - DFT Calculations and Synthesis Reveal
T2 - Key Intermediates, Omitted Mechanisms, and Unsymmetrical Bimane Products
AU - Oded, Bat El
AU - Diskin-Posner, Yael
AU - Marks, Vered
AU - Kornweitz, Haya
AU - Grynszpan, Flavio
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2023/10/16
Y1 - 2023/10/16
N2 - Theoretical and experimental mixed approaches are complementary and valuable. Our DFT calculations support the mechanism suggested by Kosower, adding to it a key diaziridine intermediate that determines the relative product distribution of this reaction. Our results are consistent with the formation of the diazoketene intermediate as the rate-limiting step. Based on curve fittings, first or second-order kinetics cannot be ruled out. This may indicate that more than one mechanism is simultaneously at play in this transformation. This unexpected outcome led us to study an alternative cyclopropenone intermediate. Although cyclopropenone is not likely to be formed under thermal conditions, adding it to the reaction mixture results in bimane structures. The most staggering finding from this investigation was the unanticipated generation of the unsymmetrical anti-(Me,Me)(Ph,Ph)bimane. The optimization of this route towards unsymmetrical bimanes will require additional investigation.
AB - Theoretical and experimental mixed approaches are complementary and valuable. Our DFT calculations support the mechanism suggested by Kosower, adding to it a key diaziridine intermediate that determines the relative product distribution of this reaction. Our results are consistent with the formation of the diazoketene intermediate as the rate-limiting step. Based on curve fittings, first or second-order kinetics cannot be ruled out. This may indicate that more than one mechanism is simultaneously at play in this transformation. This unexpected outcome led us to study an alternative cyclopropenone intermediate. Although cyclopropenone is not likely to be formed under thermal conditions, adding it to the reaction mixture results in bimane structures. The most staggering finding from this investigation was the unanticipated generation of the unsymmetrical anti-(Me,Me)(Ph,Ph)bimane. The optimization of this route towards unsymmetrical bimanes will require additional investigation.
KW - DFT
KW - bimane
KW - cyclopropenone
KW - mechanism
KW - unsymmetric
UR - http://www.scopus.com/inward/record.url?scp=85171539823&partnerID=8YFLogxK
U2 - 10.1002/ejoc.202300697
DO - 10.1002/ejoc.202300697
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AN - SCOPUS:85171539823
SN - 1434-193X
VL - 26
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
IS - 39
M1 - e202300697
ER -