Role of Noncovalent Interactions in Inducing High Enantioselectivity in an Alcohol Reductive Deoxygenation Reaction Involving a Planar Carbocationic Intermediate

化学 碳阳离子 亲核细胞 除氧 对映选择合成 硼烷 非共价相互作用 催化作用 磷酰胺 还原消去 电泳剂 组合化学 有机化学 分子 氢键 寡核苷酸 生物化学 DNA
作者
Supratim Ghosh,Avtar Changotra,David A. Petrone,Mayuko Isomura,Erick M. Carreira,Raghavan B. Sunoj
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:145 (5): 2884-2900 被引量:17
标识
DOI:10.1021/jacs.2c10975
摘要

The involvement of planar carbocation intermediates is generally considered undesirable in asymmetric catalysis due to the difficulty in gaining facial control and their intrinsic stability issues. Recently, suitably designed chiral catalyst(s) have enabled a guided approach of nucleophiles to one of the prochiral faces of carbocations affording high enantiocontrol. Herein, we present the vital mechanistic insights from our comprehensive density functional theory (B3LYP-D3) study on a chiral Ir-phosphoramidite-catalyzed asymmetric reductive deoxygenation of racemic tertiary α-substituted allenylic alcohols. The catalytic transformation relies on the synergistic action of a phosphoramidite-modified Ir catalyst and Bi(OTf)3, first leading to the formation of an Ir-π-allenyl carbocation intermediate through a turn-over-determining SN1 ionization, followed by a face-selective hydride transfer from a Hantzsch ester analogue to yield an enantioenriched product. Bi(OTf)3 was found to promote a significant number of ionic interactions as well as noncovalent interactions (NCIs) with the catalyst and the substrates (allenylic alcohol and Hantzsch ester), thus providing access to a lower energy route as compared to the pathways devoid of Bi(OTf)3. In the nucleophilic addition, the chiral induction was found to depend on the number and efficacy of such key NCIs. The curious case of reversal of enantioselectivity, when the α-substituent of the allenyl alcohol is changed from methyl to cyclopropyl, was identified to originate from a change in mechanism from an enantioconvergent pathway (α-methyl) to a dynamic kinetic asymmetric transformation (α-cyclopropyl). These molecular insights could lead to newer strategies to tame tertiary carbocations in enantioselective reactions using suitable combinations of catalysts and additives.
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