Titanium-catalyzed highly stereoselective anti-Markovnikov intermolecular hydroalkoxylation of alkynes to prepare Z-enol ethers

Literature Information

Publication Date 2023-11-15
DOI 10.1039/D3OB01514A
Impact Factor 3.876
Authors

Yang Wang, Biao Ma, Yingning Mao, Zhihui Wang, Jinsong Peng, Chunxia Chen, Zhanyu Li


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Abstract

Enol ethers are essential synthetic frameworks and widely applied in organic synthesis; however, high regio- and stereo-selective access to enol ethers remains challenging. Herein, we report a titanium-catalyzed stereospecific anti-Markovnikov hydroalkoxylation reaction of alkynes for the synthesis of Z-enol ethers with excellent functional group tolerance and yields. Mechanistic studies showed that the titanium coordinates with the alkyne and then an oxygen anion attacks the π-bond of the alkyne from the backside to provide a trans-oxygen metallation intermediate, which accounts for the high Z-stereoselectivity. Furthermore, Z-enol ethers could be applied as a kind of synthon for late-stage transformations and gram-scale synthesis, which demonstrates their potential value in organic synthesis.

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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry
CiteScore: 3.4
Self-citation Rate: 10.3%
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Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.

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