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铑氢化物催化的 C═C 键的高选择性加氢。

Highly Selective Hydrogenation of C═C Bonds Catalyzed by a Rhodium Hydride.

机构信息

Department of Chemistry, Columbia University, 3000 Broadway, New York City, New York 10027, United States.

Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, United States.

出版信息

J Am Chem Soc. 2021 Jun 30;143(25):9657-9663. doi: 10.1021/jacs.1c04683. Epub 2021 Jun 18.

DOI:10.1021/jacs.1c04683
PMID:34142805
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9366878/
Abstract

Under mild conditions (room temperature, 80 psi of H) Cp*Rh(2-(2-pyridyl)phenyl)H catalyzes the selective hydrogenation of the C═C bond in α,β-unsaturated carbonyl compounds, including natural product precursors with bulky substituents in the β position and substrates possessing an array of additional functional groups. It also catalyzes the hydrogenation of many isolated double bonds. Mechanistic studies reveal that no radical intermediates are involved, and the catalyst appears to be homogeneous, thereby affording important complementarity to existing protocols for similar hydrogenation processes.

摘要

在温和条件下(室温,80psi 的 H),Cp*Rh(2-(2-吡啶基)苯基)H 催化 α,β-不饱和羰基化合物的 C═C 键的选择性加氢,包括在β位具有大取代基的天然产物前体和具有一系列额外官能团的底物。它还催化许多孤立双键的加氢。机理研究表明,没有自由基中间体参与,催化剂似乎是均相的,从而为类似氢化过程的现有方案提供了重要的补充。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/3ad4217ef282/nihms-1827762-f0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/eeb64ba99d13/nihms-1827762-f0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/d4cc7e32248d/nihms-1827762-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/430a1c1635e7/nihms-1827762-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/e7680c5b1b42/nihms-1827762-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/e5d680677f0a/nihms-1827762-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/9e734e437f77/nihms-1827762-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/3ad4217ef282/nihms-1827762-f0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/eeb64ba99d13/nihms-1827762-f0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/d4cc7e32248d/nihms-1827762-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/430a1c1635e7/nihms-1827762-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/e7680c5b1b42/nihms-1827762-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/e5d680677f0a/nihms-1827762-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/9e734e437f77/nihms-1827762-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fdc5/9366878/3ad4217ef282/nihms-1827762-f0007.jpg

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