Diastereoselective Radical Hydroacylation of Alkylidenemalonates with Aliphatic Aldehydes Initiated by Photolysis of Hypervalent Iodine(III) Reagents.
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.
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto, 606-8502, Japan), Fax: (+81)75-753-4041.
Sermadurai
S
Selvakumar
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto, 606-8502, Japan), Fax: (+81)75-753-4041.
Ryu
R
Sakamoto
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto, 606-8502, Japan), Fax: (+81)75-753-4041. maruoka@kuchem.kyoto-u.ac.jp.
Keiji
K
Maruoka
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D007202:Indicators and Reagents / Q000737:chemistry*; D007455:Iodine / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010782:Photolysis
D000447:Aldehydes; D007202:Indicators and Reagents; D007783:Lactones; C000611461:methyleneolactocin; D007455:Iodine
diastereoselectivity; hydroacylation; hypervalent iodine; photolysis; radical reactions