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Acylation Reactions of Dibenzo-7-phosphanorbornadiene: DFT Mechanistic Insights.

ABSTRACT: Extensive DFT calculations provide deep mechanistic insights into the acylation reactions of tert-butyl dibenzo-7-phosphanobornadiene with PhCOX (X=Cl, Br, I, OTf) in CH₂Cl₂ solution. Such reactions are initialized by the nucleophilic P⋅⋅⋅C attack to the carbonyl group to form the acylphosphonium intermediate A⁺ together with X^- anion, followed either by nucleophilic X^-⋅⋅⋅P attack (X=Cl, Br, and I) toward A⁺ to eliminate anthracene or by slow rearrangement or decomposition of A⁺ (X=OTf). In contrast to the first case (X=Cl) that is rate-limited by the initial P⋅⋅⋅C attack, other reactions are rate-limited by the second X^-⋅⋅⋅P attack for X=Br and I and even thermodynamically prevented for X=OTf, leading to isolable phosphonium salts. The rearrangement of phosphonium A⁺ is initiated by a P-C bond cleavage, followed either by sequential proton-shifts to form anthracenyl acylphosphonium or by deprotonation with additional base Et₃N to form neutral anthracenyl acylphosphine. Our DFT results strongly support the separated acylphosphonium A⁺ as the key reaction intermediate that may be useful for the transfer of acylphosphenium in general.

SUBMITTER: Qu ZW

PROVIDER: S-EPMC6594351 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Acylation Reactions of Dibenzo-7-phosphanorbornadiene: DFT Mechanistic Insights.

Qu Zheng-Wang ZW Zhu Hui H Grimme Stefan S

ChemistryOpen 20190626 6

Extensive DFT calculations provide deep mechanistic insights into the acylation reactions of tert-butyl dibenzo-7-phosphanobornadiene with PhCOX (X=Cl, Br, I, OTf) in CH2Cl2 solution. Such reactions are initialized by the nucleophilic P⋅⋅⋅C attack to the carbonyl group to form the acylphosphonium intermediate A+ together with X- anion, followed either by nucleophilic X-⋅⋅⋅P attack (X=Cl, Br, and I) toward A+ t ...[more]

PMID: 31293872

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Acylation Reactions of Dibenzo-7-phosphanorbornadiene: DFT Mechanistic Insights.

Publications

Acylation Reactions of Dibenzo-7-phosphanorbornadiene: DFT Mechanistic Insights.

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