TY - JOUR
T1 - Concerted versus ionic mechanisms of the α and γ extensions in uncatalyzed Mukaiyama reaction between β,γ-unsaturated bis silyl ketene acetal and benzaldehyde
T2 - A DFT study
AU - Hadj Mohamed, Slim
AU - Champagne, Benoît
N1 - Publisher Copyright:
© 2021 Elsevier B.V.
PY - 2021/10
Y1 - 2021/10
N2 - The uncatalyzed regioselective Mukaiyama aldol reaction between β,γ-unsaturated bis silyl ketene acetal and benzaldehyde has been studied theoretically using density functional theory with the M06-2X exchange–correlation functional. These DFT calculations mostly demonstrate that (i) the α and γ adducts in uncatalyzed Mukaiyama reaction can proceed through two mechanisms, ionic and concerted, (ii) the concerted mechanism is favored for the α adduct and it is disfavored for the γ adduct, (iii) under 12 and 17 kbar, the α adduct reaction path is below the γ adduct reaction path whereas if the pressure decreases to 5 kbar, the opposite is obtained.
AB - The uncatalyzed regioselective Mukaiyama aldol reaction between β,γ-unsaturated bis silyl ketene acetal and benzaldehyde has been studied theoretically using density functional theory with the M06-2X exchange–correlation functional. These DFT calculations mostly demonstrate that (i) the α and γ adducts in uncatalyzed Mukaiyama reaction can proceed through two mechanisms, ionic and concerted, (ii) the concerted mechanism is favored for the α adduct and it is disfavored for the γ adduct, (iii) under 12 and 17 kbar, the α adduct reaction path is below the γ adduct reaction path whereas if the pressure decreases to 5 kbar, the opposite is obtained.
KW - DFT
KW - Reaction mechanism
KW - Regioselectivity
KW - α adduct Mukaiyama reaction
KW - γ adduct Mukaiyama reaction
UR - http://www.scopus.com/inward/record.url?scp=85113615971&partnerID=8YFLogxK
U2 - 10.1016/j.comptc.2021.113395
DO - 10.1016/j.comptc.2021.113395
M3 - Article
AN - SCOPUS:85113615971
SN - 2210-271X
VL - 1204
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
M1 - 113395
ER -