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Predicting phosphirane air stability using density functional theory
Author(s) -
Gaston Jayden J.,
McCosker Patrick M.,
Yu Haibo,
Keller Paul A.
Publication year - 2020
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4110
Subject(s) - chemistry , density functional theory , stability (learning theory) , computational chemistry , simplicity , combinatorial chemistry , biochemical engineering , computer science , philosophy , epistemology , machine learning , engineering
Phosphorus 3‐membered heterocycles, phosphiranes, provide an interesting synthetic scaffold with a potentially diverse range of reactions that are currently underexplored. This is in part due to their difficulty in synthesis, with many products and intermediates containing low air stability. With the application and extension of a density functional theory (DFT) model to phosphiranes by calculation at the UB3LYP/6‐31G(d) level of their radical cation singly occupied molecular orbital (SOMO), a correlation between calculated and relative experimental air stability has been demonstrated. The model also accounts for the stability of many synthesised substituted and unsubstituted phosphiranes and has allowed new synthetic targets to be identified, in particular, 1‐(2,4,6‐tri‐tert‐butoxyphenyl)phosphirane exhibited high theoretical air stability. Because of the simplicity and efficiency of the model, its application enables phosphiranes to be screened for high bench stability, providing accessibility for their use in synthetic chemistry, in turn, realising the potential for incorporation of phosphiranes into complex synthetic strategies.