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Chinese Journal of Organic Chemistry >

2023 , Vol. 43 >Issue 10: 3608 - 3613

DOI: https://doi.org/10.6023/cjoc202308009

Theoretical Study of How Electronic Effect of Substituent Affects Regioselectivity of C—Si Reductive Elimination

  • Ju Peng ,
  • Xiaoqian He ,
  • Li-Li Liao ,
  • Ruopeng Bai ,
  • Yu Lan
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  • a School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331
    b Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou 450001
† These authors contributed equally to this work
*E-mail: ;
;

Received date: 2023-08-11

  Revised date: 2023-08-29

  Online published: 2023-08-31

Supported by

National Natural Science Foundation of China(22003006); National Natural Science Foundation of China(22201027); National Natural Science Foundation of China(22271034); China Postdoctoral Science Foundation(2021M700578)

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Abstract

Regioselectivity adjustment is one of the key research fields in organic chemistry, and electronic effect is the key factor for adjustment. In this work, density functional theory (DFT) calculation was carried out to investigate how electronic effect of substituent affects regioselectivity in the reductive elimination step. Palladium-catalyzed annulation of silacyclo- butanes and 2-iodobiarenes was selected as model reaction, and detailed reaction mechanism is illustrated. The results shows that the reaction undergoes Pd—I bond oxidative addition, concerted metalation deprotonation (CMD), Pd—Si bond oxidative addition, and reductive elimination process to synthesize eight-membered silacycles, and C—Si bond reductive elimination is the rate determining step. Study of electronic effect in Pd(IV) reductive elimination transition state shows that when asymmetrically substituted 2-iodobyphenyl is used as substrate, electron density of aromatic ring is the main factor to control regioselectivity. Groups with higher electron density have higher priority for reductive elimination, and this is in accordance with electron flow in this elementary reaction.

Key words： electronic effect; regioselectivity; reductive elimination; density functional theory

Cite this article

Ju Peng , Xiaoqian He , Li-Li Liao , Ruopeng Bai , Yu Lan . Theoretical Study of How Electronic Effect of Substituent Affects Regioselectivity of C—Si Reductive Elimination[J]. Chinese Journal of Organic Chemistry, 2023 , 43(10) : 3608 -3613 . DOI: 10.6023/cjoc202308009

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