Theoretical study of a derivative of chlorophosphine with aliphatic and aromatic Grignard reagents: SN2@P or the novel SN2@Cl followed by SN2@C?

被引：0

作者：

Savoo, Nandini ^{[1
]}

Rhyman, Lydia ^{[1
,2
]}

Ramasami, Ponnadurai ^{[1
,2
]}

机构：

[1] Univ Mauritius, Fac Sci, Dept Chem, Computat Chem Grp, Reduit 80837, Mauritius

[2] Univ Johannesburg, Ctr Nat Prod Res, Dept Chem Sci, Doornfontein Campus, ZA-2028 Johannesburg, South Africa

来源：

RSC ADVANCES | 2022年 / 12卷 / 15期

关键词：

MAIN-GROUP THERMOCHEMISTRY; NUCLEOPHILIC-SUBSTITUTION; DENSITY FUNCTIONALS; NONCOVALENT INTERACTIONS; MP2; ENERGY; AB-INITIO; TRANSITION; STEREOCHEMISTRY; PERFORMANCE; FREQUENCIES;

D O I：

10.1039/d2ra00258b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The proposed S(N)2 reactions of a hindered organophosphorus reactant with aliphatic and aromatic nucleophiles [Ye et al., Org. Lett., 2017, 19, 5384-5387] were studied theoretically in order to explain the observed stereochemistry of the products. Our computations (using B3LYP as the functional) indicate that the reaction with the aliphatic nucleophile occurs through a backside S(N)2@P pathway while the reaction with the aromatic nucleophile proceeds through a novel S(N)2@Cl mechanism, followed by a frontside S(N)2@C mechanism.

引用

页码：9130 / 9138

页数：9

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