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. 2022 Jul 15;12(14):8164-8174.
doi: 10.1021/acscatal.2c02444. Epub 2022 Jun 23.

Enantioselective Metal-Catalyzed Reductive Coupling of Alkynes with Carbonyl Compounds and Imines: Convergent Construction of Allylic Alcohols and Amines

Eliezer Ortiz  1 , Jonathan Shezaf  1 , Yu-Hsiang Chang  1 , Michael J Krische  1
Affiliations

Enantioselective Metal-Catalyzed Reductive Coupling of Alkynes with Carbonyl Compounds and Imines: Convergent Construction of Allylic Alcohols and Amines

Eliezer Ortiz et al. ACS Catal. .

Abstract

The use of alkynes as vinylmetal pronucleophiles in intermolecular enantioselective metal-catalyzed carbonyl and imine reductive couplings to form allylic alcohols and amines is surveyed. Related hydrogen auto-transfer processes, wherein alcohols or amines serve dually as reductants and carbonyl or imine proelectrophiles, also are cataloged, as are applications in target-oriented synthesis. These processes represent an emerging alternative to the use of stoichiometric vinylmetal reagents or Nozaki-Hiyama-Kishi (NHK) reactions in carbonyl and imine alkenylation.

Keywords: Alkyne; Allylic Alcohol; Allylic Amine; Enantioselective; Hydrogen Transfer; Reductive Coupling.

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Figures

Figure 1.
Figure 1.
Strategies for catalytic enantioselective vinylation of carbonyl compounds and imines.
Scheme 1.
Scheme 1.
Enantioselective rhodium-catalyzed reductive coupling of 1,3-enynes or 1,3-diynes with activated aldehydes or ketones mediated by hydrogen.
Scheme 2.
Scheme 2.
Mechanism for rhodium-catalyzed reductive coupling of conjugated alkynes with activated carbonyl compounds mediated by hydrogen.
Scheme 3.
Scheme 3.
Diastereoselective rhodium-catalyzed reductive coupling of 1,3-enynes or 1,3-diynes with ethyl (N-tert-butanesulfinyl)iminoacetate mediated by hydrogen.
Scheme 4.
Scheme 4.
Synthesis of bryostatin 7 and selected seco-B-ring analogs via asymmetric rhodium-catalyzed reductive coupling of 1,3-enynes with glyoxals mediated by hydrogen.
Scheme 5.
Scheme 5.
Enantioselective nickel-catalyzed reductive coupling of 1,3-enynes with aldehydes or ketones mediated by triethylborane.
Scheme 6.
Scheme 6.
Enantioselective and diastereoselective rhodium-catalyzed reductive coupling of acetylene with carbonyl compounds or imines mediated by hydrogen.
Scheme 7.
Scheme 7.
Enantioselective iridium-catalyzed reductive coupling of nonconjugated alkynes with N-arylsulfonyl aldimines mediated by hydrogen.
Scheme 8.
Scheme 8.
Enantioselective and diastereoselective ruthenium-catalyzed reductive coupling of 2-butyne with aldehydes via hydrogen auto-transfer from alcohol reactants.
Scheme 9.
Scheme 9.
Enantioselective and diastereoselective cobalt-catalyzed reductive coupling of alkynes with aldehydes mediated by Hantzsch ester.
Scheme 10.
Scheme 10.
Enantioselective nickel-catalyzed reductive coupling of alkynes with aldehydes mediated by boranes or silanes.
Scheme 11.
Scheme 11.
Natural products prepared via nickel-catalyzed alkyne-carbonyl reductive coupling.
Scheme 12.
Scheme 12.
Enantioselective nickel-catalyzed reductive coupling of alkynes with aldehydes or aldimines via hydrogen auto-transfer from alcohol or amine reactants, respectively.
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