title: The Mukaiyama aldol reaction of in situ generated nitrosocarbonyl compounds: selective C-N bond formation and N-O bond cleavage in one-pot for α-amination of ketones.
abstract: A practical protocol for the α-amination of ketones (up to 99% yield) has been developed via the Mukaiyama aldol reaction of in situ generated nitrosocarbonyl compounds. The reaction with silyl enol ethers having a disilane (-SiMe2TMS) backbone proceeded not only with perfect N-selectivity but concomitant N-O bond cleavage was also accomplished. Such a cascade of C-N bond formation and N-O bond cleavage in a single step was heretofore unknown in the field of nitrosocarbonyl chemistry. A very high diastereoselectivity (dr = 19 : 1) was accomplished using (-)-menthol derived chiral nitrosocarbonyl compounds.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, Tamil Nadu, India. mbaidya@iitm.ac.in.
authors.forename: Isai
authors.initials: I
authors.lastname: Ramakrishna
authors.forename: Gowri Sankar
authors.initials: GS
authors.lastname: Grandhi
authors.forename: Harekrishna
authors.initials: H
authors.lastname: Sahoo
authors.forename: Mahiuddin
authors.initials: M
authors.lastname: Baidya
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D000586:Amination; D003300:Copper / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D009603:Nitroso Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry
chemical_list: D000097:Acetonitriles; D007659:Ketones; D009603:Nitroso Compounds; D011725:Pyridines; D003300:Copper; C029892:cupric chloride; D010100:Oxygen; C032159:acetonitrile