1164-92-7Relevant articles and documents
Controlling the reactive state through cation binding: Photochemistry of enones within zeolites
Uppili, Sundararajan,Takagi, Shinsuke,Sunoj,Lakshminarasimhan,Chandrasekhar,Ramamurthy
, p. 2079 - 2083 (2007/10/03)
The nature of the lowest triplet state of enones is altered by the cations present within Y zeolites. Alkali metal ions, such as Li+, are predicted to interact with the carbonyl unit of enones in a collinear fashion and significantly lower both the p-type n and π-2 orbitals. Excited state energies, estimated at the CIS(D)/6-31+G* level, show that the lowest triplet is n-π* in character for the enones, but switch to π-π* on coordination with Li+. Observed product distribution within zeolite is consistent with this theoretical prediction.
Facial selective photoreduction of steroids: Role of zeolites
Jayathirtha Rao,Rajan Uppili,Corbin,Schwarz,Lustig,Ramamurthy
, p. 2480 - 2481 (2007/10/03)
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NAD(P)H Models XV. Reduction of Δ4-3-ketosteroids via their iminium salts, by 1,4-dihydropyridine derivatives
Gase, Ronald A.,Pandit, Upendra K.
, p. 334 - 340 (2007/10/02)
Pyrrolidinium salts derived from a series of 17-substituted Δ4-3-ketosteroids are reduced by 1-benzyl-1,4-dihydronicotinamide (BNAH) and 2,6-dimethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine (Hantzsch ester, 1 eq.) to the corresponding isomeric 5α- and 5β-enamines which hydrolyse to the corresponding 3-ketosteroids.In the case of the Hantzsch ester reduction, proton transfer from the oxidized Hantzsch ester to the enamine results in the formation of iminium salts, which are further reduced to the corresponding ammonium salts.Mechanistic, stereochemical and biochemical implications of the reactions are discussed.