Racemization mechanism of lithium tert‐butylphenylphosphido‐borane: A kinetic insight

The racemization mechanism of tert‐butylphenylphosphido‐borane is investigated experimentally and theoretically. Based on this converging approach, it is shown, first, that several phosphido‐borane molecular species coexist at the time of the reaction and, second, that one particular of both initial...

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Bibliographic Details
Published in:Chirality (New York, N.Y.) N.Y.), 2022-01, Vol.34 (1), p.27-33
Main Authors: Fortrie, Rémy, Gatineau, David, Hérault, Damien, Béal, Aurélie, Naubron, Jean‐Valère, Giordano, Laurent, Buono, Gérard
Format: Article
Language:English
Subjects:
Boranes
Chemical Sciences
chiral ligand
complex reaction scheme analysis
Convergence
DFT modeling
kinetic modeling
kinetic resolution
Kinetics
Lithium
Phosphides
Racemization
Stereoisomerism
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Summary:The racemization mechanism of tert‐butylphenylphosphido‐borane is investigated experimentally and theoretically. Based on this converging approach, it is shown, first, that several phosphido‐borane molecular species coexist at the time of the reaction and, second, that one particular of both initially assumed reactive routes most significantly contribute to the overall racemization process. From our converging modeling and experimental measurement, it comes out that the most probable species to be here encountered is a phosphido‐borane‐Li (THF)2 neutral solvate, whose P‐stereogenic center monomolecular inversion through a Y‐shaped transition structure (ΔrG°≠: 81 kJ mol−1) brings the largest contribution to the racemization process. Experimental and theoretical investigations of lithium phosphido‐borane racemization kinetic.
ISSN:0899-0042
1520-636X
DOI:10.1002/chir.23383