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Synfacts 2025; 21(01): 40
DOI: 10.1055/a-2467-4960
Metals in Synthesis

Nickel Hydride Catalyzed Enantioselective Synthesis of Alkenyl Cyclobutanols from 1,4-Alkynones

Contributor(s):
Martin Oestreich 
,
Hendrik F. T. Klare 
,
Emilio Acuña Bolomey 
Li X-L, Deng J-L, Long J, Fu Y-F, Zheng Y-Q, Liu W-B *. Wuhan University and Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, P. R. China
Access to Alkenyl Cyclobutanols by Ni-Catalyzed Regio- and Enantioselective syn-Hydrometalative 4-exo-trig Cyclization of Alkynones.

Angew. Chem. Int. Ed. 2024;
DOI: 10.1002/anie.202415164
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Keywords

1,4-alkynones - asymmetric catalysis - cyclobutanols - nickel hydride catalysis

Significance

Liu and co-workers present a nickel hydride catalyzed enantioselective synthesis of alkenyl cyclobutanols from 1,4-alkynones. The latter undergo a carbonyl-directed syn-hydrometalation, followed by an enantioselective intramolecular 1,2-addition to the carbonyl group, resulting in highly enantioenriched cyclobutanols.


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Comment

Several experiments were performed to support the proposed mechanism, including kinetic studies, deuterium labelling and DFT calculations. The presence of fluorine atoms at the α-position of the carbonyl group proved to be crucial; while a CF2H group also delivered the products in good yields, alkyl and aryl substituents performed poorly.


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Publication History

Article published online:
20 December 2024

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