Ti-Catalyzed Reductive Dehydroxylative Vinylation of Tertiary Alcohols

Metal-catalyzed direct deoxygenative C­(sp3)–C­(sp2) coupling of alcohols is synthetically appealing, but it remains a particular challenge for the synthetic community. Herein, we demonstrate a radical dehydroxylative vinylation reaction of tertiary alcohols by Ti catalysis and, thus, establish a me...

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Bibliographic Details
Published in:ACS catalysis 2022-01, Vol.12 (2), p.1018-1023
Main Authors: Xie, Hao, Wang, Sheng, Wang, Yuquan, Guo, Peng, Shu, Xing-Zhong
Format: Article
Language:English
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Summary:Metal-catalyzed direct deoxygenative C­(sp3)–C­(sp2) coupling of alcohols is synthetically appealing, but it remains a particular challenge for the synthetic community. Herein, we demonstrate a radical dehydroxylative vinylation reaction of tertiary alcohols by Ti catalysis and, thus, establish a method for the construction of vinylated all-carbon quaternary centers. The reaction proceeds under mild conditions and tolerates various functionalities, including Ar–Bpin, Ar–SiMe3, alkyl chloride, phenol, nitrile, ester, furan, and thiophene. The reaction works with various vinyl halides, including fluorides, chlorides, bromides, and iodides. The use of a mixture of trans- and cis-haloalkenes gives the same trans products. The selectivity profiles were investigated among the vinyl and aryl electrophiles and among the different classes of alcohols.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.1c05530