Sökning: onr:"swepub:oai:DiVA.org:su-228130" >
Mechanism of Asymme...
Mechanism of Asymmetric Homologation of Alkenylboronic Acids with CF3-Diazomethane via Borotropic Rearrangement
-
- Biosca, Maria (författare)
- Stockholms universitet,Institutionen för organisk kemi
-
- Szabó, Kálmán J. (författare)
- Stockholms universitet,Institutionen för organisk kemi
-
- Himo, Fahmi, 1973- (författare)
- Stockholms universitet,Institutionen för organisk kemi
-
(creator_code:org_t)
- 2024
- 2024
- Engelska.
-
Ingår i: Journal of Organic Chemistry. - 0022-3263 .- 1520-6904. ; 89:7, s. 4538-4548
- Relaterad länk:
-
https://doi.org/10.1...
-
visa fler...
-
https://urn.kb.se/re...
-
https://doi.org/10.1...
-
visa färre...
Abstract
Ämnesord
Stäng
- Density functional theory calculations have been performed to investigate the mechanism for the BINOL-catalyzed asymmetric homologation of alkenylboronic acids with CF3-diazomethane. The reaction proceeds via a chiral BINOL ester of the alkenylboronic acid substrate. The calculations reveal a complex scenario for the formation of the chiral BINOL-alkenylboronate species, which is the key intermediate in the catalytic process. The aliphatic alcohol additive plays an important role in the reaction. This study provides a rationalization of the stereoinduction step of the reaction, and the enantioselectivity is mainly attributed to the steric repulsion between the CF3 group of the diazomethane reagent and the γ-substituent of the BINOL catalyst. The complex potential energy surface obtained by the calculations is analyzed by means of microkinetic simulations.
Ämnesord
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
Hitta via bibliotek
Till lärosätets databas