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CAS: 1647165-16-9
MF: C28H31O4I
MW: 558.44734
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REPORT BY

Keiji Maruoka

Kyoto University
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Co-reporter: Dr. Shin A. Moteki;Asuka Usui;Dr. Sermadurai Selvakumar;Dr. Tiexin Zhang ;Dr. Keiji Maruoka
pp: 11060-11064
Publication Date(Web):
DOI: 10.1002/anie.201406513

Abstract

Direct acyl radical formation of linear aldehydes (RCH2-CHO) and subsequent hydroacylation with electron-deficient olefins can be effected with various types of metal and nonmetal catalysts/reagents. In marked contrast, however, no successful reports on the use of branched aldehydes have been made thus far because of their strong tendency of generating alkyl radicals through the facile decarbonylation of acyl radicals. Here, use of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes, thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent, which is a rare example on the generation of radicals in hypervalent iodine chemistry.

Co-reporter: Sermadurai Selvakumar;Ryu Sakamoto ; Keiji Maruoka
pp: 6552-6555
Publication Date(Web):
DOI: 10.1002/chem.201600425

Abstract

Diastereoselective radical hydroacylation of chiral alkylidenemalonates with aliphatic aldehydes is realized by the combination of a hypervalent iodine(III) reagent and UV-light irradiation. The reaction is initiated by the photolysis of hypervalent iodine(III) reagents under mild, metal-free conditions, and is the first example of diastereoselective addition of acyl radicals to olefins to afford chiral ketones in a highly stereoselective fashion. The obtained optically active ketones are useful chiral synthons, as exemplified by the short formal synthesis of (−)-methyleneolactocin.