105729-06-4Relevant articles and documents
Metal-Metal Exchange of α-Metallo Ketones. Novel Formation of α-Acyl Anion and α-Keto Carbonium Ion Equivalents from (Aryl)phenacyl TlIII, PbIV, and HgII Systems
Moriarty, Robert M.,Penmasta, Raju,Prakash, Indra,Awasthi, Alok K.
, p. 1022 - 1025 (1988)
The novel class of α-metallo ketones RCOCH2TlIIItolyl(OCOCF3) where R = phenyl, substituted phenyl, thienyl, pyridinyl, and tert-butyl have been synthesized and characterized by 1H NMR and 13C NMR.These compounds serve as anion equivalents in the TiCl4-mediated aldol condensation.Metal-metal exchange with iodosylbenzene or lead tetraacetate leads to α-nucleophilic substitution derived from the formal α-keto carbonium ion equivalent.The corresponding p-CH3OC6H4COCH2PbIVC6H4OCH3-p-(OCOCH3)2 and (p-CH3OC6H4COCH2)2HgII analogues were synthesized and shown to likewise behave as either enolate anion or α-keto carbonium ion equivalents upon metal-metal exchange with TiIV, PbIV, or IIII.The importance of this work is that the range of reactivity of α-metallo ketones may be selectively adjusted by metal-metal or metal-metalloid exchange.
Hypervalent iodine oxidation of silyl enol ethers under Lewis acid conditions in methanol. A general route to α-methoxy ketones
Moriarty, Robert M.,Prakash, Om,Duncan, Michael P.,Vaid, Radhe K.,Musallam, Hikmat A.
, p. 150 - 153 (1987)
Hypervalent iodine oxidation of various silyl enol ethers (aromatic, heteroaromatic, aliphatic) using iodosobenzene-boron trifluoride etherate in methanol leads to α-methoxylation of ketones in high yields. The scope and mechanism of the reaction are discussed.
