Recent Advances in Ring‐Opening Functionalization of Cycloalkanols by C–C σ‐Bond Cleavage

• Published in: Chemical record Vol. 18; no. 6; pp. 587 - 598
• Main Authors: Wu, Xinxin, Zhu, Chen
• Format: Journal Article
• Language: English
• Published: United States Wiley Subscription Services, Inc 01.06.2018
• Subjects: Chemical bonds; Cleavage; Cycloalkanol; C−C bond activation; Ductile-brittle transition; Fracture mechanics; ketone; Ketones; Organic chemistry; Polycyclic aromatic hydrocarbons; radical reaction; Ring opening; ring-opening reaction; ketone; radical reaction; Cycloalkanol; C−C bond activation; ring-opening reaction
• ISSN: 1527-8999; 1528-0691
• DOI: 10.1002/tcr.201700090

Cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C−C bonds. Direct functionalization of cyclobutanols to build up other chemical bonds (e. g., C−F, C−Cl, C−Br, C−N, C−S, C−Se, C−C, etc.) has been achieved by using the ring‐opening strategy. Mechanistically, the C−C cleavage of cyclobutanols can be involved in two pathways: (a) transition‐metal catalyzed β‐carbon elimination; (b) radical‐mediated ‘radical clock’‐type ring opening. The recent advances of our group for the ring‐opening functionalization of tertiary cycloalkanols are described in this account. C−C σ‐bond cleavage: cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C−C bonds. The recent advances in the ring‐opening functionalization of tertiary cycloalkanols are summarized in this account.