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. 2021 Apr 22;6(17):11740-11749.
doi: 10.1021/acsomega.1c01083. eCollection 2021 May 4.

Substrate-Controlled Cu(OAc)2-Catalyzed Stereoselective Semi-Reduction of Alkynes with MeOH as the Hydrogen Source

Jiuzhong Huang  1 , Xiaoning Li  2 , Huiling Wen  1 , Lu Ouyang  1 , Nianhua Luo  1 , Jianhua Liao  1 , Renshi Luo  1
Affiliations

Substrate-Controlled Cu(OAc)2-Catalyzed Stereoselective Semi-Reduction of Alkynes with MeOH as the Hydrogen Source

Jiuzhong Huang et al. ACS Omega. .

Abstract

A substrate-controlled stereoselective semi-reduction of alkynes with MeOH as the hydrogen source has been developed, and readily available Cu(OAc)2 (copper acetate) is utilized as an optimal catalyst. The detailed investigation of the mechanism revealed distinct catalytic processes for the (Z)- and (E)-alkenes, respectively. As a result, a diversity of alkynes (including terminal, internal alkynes etc.) were compatible under the mild reaction conditions. Furthermore, the high proportion of deuterium in Z-alkenes (up to 96%) was obtained using d 4-methanol as a solvent.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Stereodivergent Catalytic Transfer Hydrogenation (CTH) of Alkynes
Figure 1
Figure 1
Synthesis of deuterated (Z)-alkenes. Conditions: substrate 1 (0.3 mmol), anhydrous Cu(OAc)2 (10 mol %), 4,4′-bpy (10 mol %), B2pin2 (1.0 equiv), CD3OD (2.0 mL) under a N2 atmosphere at 60 °C for 18 h; Isolated yields. Unless otherwise noted, products Z/E > 20:1. The deuterium content was determined by 1H NMR.
Scheme 2
Scheme 2. Effect of Various Equivalents of B2pin2 for the Transformation of Possible Intermediates
Scheme 3
Scheme 3. Control Experiments
Scheme 4
Scheme 4. Proposed Mechanism
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