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Synthesis of 1,4-diketones


Recent Literature

A Ru2+-photocatalyzed, visible-light-mediated ATRA reaction of α-bromoketones with alkyl enol ethers provides 1,4-ketoaldehydes, 1,4-diketones, and 1,4-ketoesters, which are difficult to access. This method enables the construction of secondary, tertiary, and challenging quaternary centers. A construction of substituted pyrroles is also described.
W. H. García-Santos, H. B. Mateus-Ruiz, A. Cordero-Vargas, Org. Lett., 2019, 21, 4092-4096.

A visible-light-induced radical coupling reaction of silyl enol ethers with α-bromocarbonyl compounds provides 1,4-dicarbonyls. The reaction was effectively accelerated using an inexpensive organic dye (eosin Y) as a photoredox catalyst.
N. Esumi, K. Suzuki, Y. Nishimoto, M. Yasuda, Org. Lett., 2016, 18, 5704-5707.

In a Co-catalyzed reaction for the construction of 1,4-dicarbonyls, a cascade organocobalt addition/trapping/Kornblum-DeLaMare rearrangement were involved. The reaction offers easy availability of starting materials, wide substrate scope, high functionality tolerance, and operational simplicity.
F. Zhang, P. Du, J. Chen, H. Wang, Q. Luo, X. Wan, Org. Lett., 2014, 16, 1932-1935.

The perovskite colloid CsPbBr3 can selectively photocatalyze α-alkylation of aldehydes with a turnover number (TON) of over 52,000 under visible light illumination.
X. Zhu, Y. Lin, Y. Sun, M. C. Beard, Y. Yan, J. Am. Chem. Soc., 2019, 141, 733-738.

Singly occupied molecular orbital (SOMO) catalysis allows an enantioselective organocatalytic α-enolation of aldehydes. A chiral secondary amine catalyst reacts with aldehydes to form transient enamines that undergo selective one-electron oxidation to generate SOMO-activated electrophilic radical cations which are susceptible to attack by ketone-derived enol silanes.
H.-Y. Jang, J.-B. Hong, D. W. C. MacMillan, J. Am. Chem. Soc., 2007, 129, 7004-7005.

A tandem reaction consisting of a Wittig reaction-ring contraction process between α-hydroxycyclobutanone and phosphonium ylides provides highly functionalized cyclopropanecarbaldehydes in very good yield.
F. Cuccu, L. Serusi, A. Luridiana, F. Secci, P. Caboni, D. J. Aitken, A. Frongia, Org. Lett., 2019, 21, 7755-7758.