How does methanol assist the hydrogen transfer in Pd-catalyzed cyclocarbonylation of allylic alcohols? insights from a DFT study

Mawia Hassan; Xin Zhang; Wenchao Zhang; Xiaojia Guo; Biaohua Chen; Ming Lei

doi:10.1246/cl.2012.693

How does methanol assist the hydrogen transfer in Pd-catalyzed cyclocarbonylation of allylic alcohols? insights from a DFT study

Mawia Hassan^*, Xin Zhang, Wenchao Zhang, Xiaojia Guo, Biaohua Chen, Ming Lei

^*Corresponding author for this work

Beijing University of Chemical Technology

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

The carbonylation mechanisms of allylic alcohol catalyzed by [PdHCl(bppm)] complex were studied using a density functional theory (DFT) method. The results indicate that the catalytic cycle consists of three main steps: alkene insertion, CO insertion, and hydrogen transfer and product elimination. Pathways with a Pd(II) character are more favorable than that with Pd(IV) character. Methanol serves as the proton shuttle in carbonylation and reduces the energy barrier by 15.4 kcal mol1 below that without methanol assistance.

Original language	English
Pages (from-to)	693-695
Number of pages	3
Journal	Chemistry Letters
Volume	41
Issue number	7
DOIs	https://doi.org/10.1246/cl.2012.693
Publication status	Published - 2012
Externally published	Yes

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Hassan, M., Zhang, X., Zhang, W., Guo, X., Chen, B., & Lei, M. (2012). How does methanol assist the hydrogen transfer in Pd-catalyzed cyclocarbonylation of allylic alcohols? insights from a DFT study. Chemistry Letters, 41(7), 693-695. https://doi.org/10.1246/cl.2012.693

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abstract = "The carbonylation mechanisms of allylic alcohol catalyzed by [PdHCl(bppm)] complex were studied using a density functional theory (DFT) method. The results indicate that the catalytic cycle consists of three main steps: alkene insertion, CO insertion, and hydrogen transfer and product elimination. Pathways with a Pd(II) character are more favorable than that with Pd(IV) character. Methanol serves as the proton shuttle in carbonylation and reduces the energy barrier by 15.4 kcal mol1 below that without methanol assistance.",

author = "Mawia Hassan and Xin Zhang and Wenchao Zhang and Xiaojia Guo and Biaohua Chen and Ming Lei",

year = "2012",

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T1 - How does methanol assist the hydrogen transfer in Pd-catalyzed cyclocarbonylation of allylic alcohols? insights from a DFT study

AU - Hassan, Mawia

AU - Zhang, Xin

AU - Zhang, Wenchao

AU - Guo, Xiaojia

AU - Chen, Biaohua

AU - Lei, Ming

PY - 2012

Y1 - 2012

N2 - The carbonylation mechanisms of allylic alcohol catalyzed by [PdHCl(bppm)] complex were studied using a density functional theory (DFT) method. The results indicate that the catalytic cycle consists of three main steps: alkene insertion, CO insertion, and hydrogen transfer and product elimination. Pathways with a Pd(II) character are more favorable than that with Pd(IV) character. Methanol serves as the proton shuttle in carbonylation and reduces the energy barrier by 15.4 kcal mol1 below that without methanol assistance.

AB - The carbonylation mechanisms of allylic alcohol catalyzed by [PdHCl(bppm)] complex were studied using a density functional theory (DFT) method. The results indicate that the catalytic cycle consists of three main steps: alkene insertion, CO insertion, and hydrogen transfer and product elimination. Pathways with a Pd(II) character are more favorable than that with Pd(IV) character. Methanol serves as the proton shuttle in carbonylation and reduces the energy barrier by 15.4 kcal mol1 below that without methanol assistance.

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U2 - 10.1246/cl.2012.693

DO - 10.1246/cl.2012.693

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VL - 41

SP - 693

EP - 695

JO - Chemistry Letters

JF - Chemistry Letters

IS - 7

ER -

How does methanol assist the hydrogen transfer in Pd-catalyzed cyclocarbonylation of allylic alcohols? insights from a DFT study

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