Chromium-catalyzed stereodivergent E- and Z-selective alkyne hydrogenation controlled by cyclic (alkyl)(amino)carbene ligands

Ling，Liang1; Hu，Chenyang2; Long，Linhong3; Zhang，Xue1; Zhao，Lixing1; Liu，Liu Leo2; Chen，Hui3; Luo，Meiming1; Zeng，Xiaoming1

2023-12-01

10.1038/s41467-023-36677-9

Nature Communications   Impact Factor & Quartile

2041-1723

The hydrogenation of alkynes allows the synthesis of olefins, which are important feedstock for the materials, pharmaceutical, and petrochemical industry. Thus, methods that enable this transformation via low-cost metal catalysis are desirable. However, achieving stereochemical control in this reaction is a long-standing challenge. Here, we report on the chromium-catalyzed E- and Z-selective olefin synthesis via hydrogenation of alkynes, controlled by two carbene ligands. A cyclic (alkyl)(amino)carbene ligand that contains a phosphino anchor enables the hydrogenation of alkynes in a trans-addition manner, selectively forming E-olefins. With an imino anchor-incorporated carbene ligand, the stereoselectivity can be switched, giving mainly Z-isomers. This ligand-enabled geometrical stereoinversion strategy by one metal catalysis overrides common methods in control of the E- and Z-selectivity with two different metal catalysis, allowing for highly efficient and on-demand access to both E- and Z-olefins in a stereo-complementary fashion. Mechanistic studies indicate that the different steric effect between these two carbene ligands may mainly dominate the selective forming E- or Z-olefins in control of the stereochemistry.

English

NI Journal Papers

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2-s2.0-85148548876

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1.Key Laboratory of Green Chemistry & Technology,Ministry of Education,College of Chemistry,Sichuan University,Chengdu,610064,China
2.Shenzhen Grubbs Institute and Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
3.Beijing National Laboratory for Molecular Sciences (BNLMS),Key Laboratory of Photochemistry,CAS Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing,100190,China

Ling，Liang,Hu，Chenyang,Long，Linhong,et al. Chromium-catalyzed stereodivergent E- and Z-selective alkyne hydrogenation controlled by cyclic (alkyl)(amino)carbene ligands[J]. Nature Communications,2023,14(1).

Ling，Liang.,Hu，Chenyang.,Long，Linhong.,Zhang，Xue.,Zhao，Lixing.,...&Zeng，Xiaoming.(2023).Chromium-catalyzed stereodivergent E- and Z-selective alkyne hydrogenation controlled by cyclic (alkyl)(amino)carbene ligands.Nature Communications,14(1).

Ling，Liang,et al."Chromium-catalyzed stereodivergent E- and Z-selective alkyne hydrogenation controlled by cyclic (alkyl)(amino)carbene ligands".Nature Communications 14.1(2023).