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Synthesis of cyclobutanones


Recent Literature

A catalytic protio-semipinacol ring-expansion reaction for the highly enantioselective conversion of tertiary vinylic cyclopropyl alcohols into cyclobutanone products bearing α-quaternary stereogenic centers relies on the cocatalytic effect of a chiral dual-hydrogen-bond donor (HBD) with hydrogen chloride. In a stepwise mechanism, protonation of the alkene is followed by C-C bond migration.
M. A. S. Blackburn, C. C. Wagen, M. R. Bodrogean, P. M. Tadross, A. J. Bendelsmith, D. A. Kutateladze, E. N. Jacobsen, J. Am. Chem. Soc., 2023, 145, 15036-15042.

Hydroboration of 1-alkynyl-1-boronate esters and in situ transmetalation furnishes 1-alkenyl-1,1-borozinc heterobimetallic intermediates. Reaction with aldehydes and in situ cyclopropanation generates B(pin) substituted cyclopropyl carbinols with excellent diastereoselectivities. Oxidation provides trisubstituted α-hydroxycyclopropyl carbinols, that allow access to both cis- and trans-2,3-disubstituted cyclobutanones via a facile pinacol-type rearrangement.
M. M. Hussain, H. Li, N. Hussain, M. Ureņa, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2009, 131, 6516-6524.

M. M. Hussain, H. Li, N. Hussain, M. Ureņa, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2009, 131, 6516-6524.

Chemoselective C-C bond cleavages of reactive bicyclo[1.1.1]pent-1-yl alcohols (BCP-OHs) provide cyclobutanone derivatives through a base-mediated single C-C bond cleavage or α,β-unsaturated ketones by palladium-catalyzed dual C-C bond cleavage.
Y. Ma, Y. Ai, S. Yu, Synlett, 2023, 34, 149-152.

Oxidative ring expansion of methylenecyclopropanes with CAN under oxygen atmosphere was investigated. A facile conversion affording 2,2-diarylcyclobutanones occurred in good yields.
V. Nair, T. D. Suja, K. Mohanan, Synthesis, 2006, 2531-2534.

A catalytic radical process enables an asymmetric 1,4-C-H alkylation of diazoketones for stereoselective construction of cyclobutanone structures. The key to success is the optimization of the Co(II)-based metalloradical catalyst through judicious modulation of a D2-symmetric chiral amidoporphyrin ligand to adopt proper steric, electronic, and chiral environments.
J. Xie, P. Xu, Y. Zhu, J. Wang, W.-C. C. Lee, X. P. Zhang, J. Am. Chem. Soc., 2021, 143, 11337-11344.

A stereospecific gold(I)-catalyzed rearrangement of 1-alkynyl cyclobutanols and cyclopropanols provides alkylidene cycloalkanones. The reaction tolerates terminal alkynes as well as alkyl, aryl, and halo-substitution at the acetylenic position and substituents on the ring.
J. P. Markham, S. T. Staben, F. D. Toste, J. Am. Chem. Soc., 2005, 127, 9708-9709.

Visible-Light-Induced Aza-Pinacol Rearrangement: Ring Expansion of Alkylidenecyclopropanes
W.-D. Liu, G.-Q. Xu, X.-Q. Hu, P.-F. Xu, Org. Lett., 2017, 19, 6288-6291.

Halocycloalkenones are potent dienophiles in Diels-Alder cycloadditions. 2-Brominated cycloalkenone dienophiles are highly endo selective and significantly more reactive than their nonhalogenated parent compounds. A base-mediated reaction enables the facile conversion of brominated cyclobutanone Diels-Alder adducts to synthetically useful cyclopropyl derivatives.
A. G. Ross, S. D. Townsend, S. J. Danishefsky, J. Org. Chem., 2013, 78, 204-210.