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Abstract
Ketone is an important structural moiety in organic chemistry due to its wide occurrence in organic compounds and the highly transformable ability into other functionalities. Therefore, the efficient synthesis of ketones is of great significance. Recently, the ring-opening functionalization of
tert-cyclobutanols represents one of the most important approaches to synthesize γ-substituted alkyl ketones. A variety of functional groups can be efficiently introduced to the γ-position of carbonyl via the regioselective C—C bond cleavage and a new chemical bond (C—C, C—N, C—O, C—F, etc.) formation. Two major pathways might be involved in the ring-opening reactions of
tert-cyclobutanols: a) transition metals, such as Pd(Ⅱ) and Rh(Ⅰ), catalyzed β-carbon elimination of
tert-cyclobutanols, and b) radical-mediated ring opening via the single electron oxidation of
tert-cyclobutanols. The recent advances in the ring openings of
tert-cyclobutanols and the related mechanistic details are described in this review.
Contents
1 Introduction
2 Transition-metal catalyzed ring openings of tert-cyclobutanols via β-carbon elimination
2.1 Pd-catalyzed ring-opening reactions of tert-cyclobutanols
2.2 Rh-catalyzed ring-opening reactions of tert-cyclobutanols
3 Radical-mediated ring openings of tert-cyclobutanols
3.1 Oxidative ring opening of tert-cyclobutanols to construct carbon-carbon bond
3.2 Oxidative ring opening of tert-cyclobutanols to construct carbon-heteroatom bonds
4 PIDA-mediated ring-opening hydroxylation of tert-cyclobutanols via carbocation pathway
5 Conclusion and outlook
Keywords
tert-cyclobutanol
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γ-substituted ketone
/
ring opening
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C—C bond cleavage
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β-carbon elimination
/
radical
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Yan Hong, Zhu Chen.
Ring Openings of tert-Cyclobutanols: New Strategy towards the Synthesis of γ-Substituted Ketones via C—C Bond Cleavage.
Progress in Chemistry, 2016, 28(1): 1-8 DOI:10.7536/PC150906