87946-61-0Relevant academic research and scientific papers
THE CHEMISTRY OF DIPHENYLCARBENE IN POLYCRYSTALLINE (S)-2-BUTANOL. THE FORMATION OF AN ENANTIOMERICALLY PURE PRODUCT OF RADICAL-RADICAL COUPLING
Zayas, Jose,Platz, Matthew S.
, p. 3689 - 3692 (1983)
Photolysis of diphenyldiazomethane 1 in RS-2-butanol in solution between room temperature and -115 deg C gives ether 5 as only volatile product.Photolysis of 1 in polycrystalline (S)-2-butanol at -196 deg C gives 5 as well as the 5 products derived from formal CH insertion of the carbene into the matrix.Tertiary alcohol 6 was formed in 15percent yield and was shown to be enantiomerically pure.
Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C?O Bond Formation
Estopi?á-Durán, Susana,Donnelly, Liam J.,Mclean, Euan B.,Hockin, Bryony M.,Slawin, Alexandra M. Z.,Taylor, James E.
supporting information, p. 3950 - 3956 (2019/02/16)
A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C?O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.
The Formation of an Enantiomerically Pure Product of Free Radical Coupling. The Chemistry of Diphenylcarbene in Polycrystalline (S)-(+)-2-Butanol
Zayas, Jose,Platz, Matthew S.
, p. 7065 - 7069 (2007/10/02)
Photolysis of 0.1 M diphenyldiazomethane at 77 K or 137 K in solid (S)-(+)-2-butanol gives tertiary alcohol 9 along with other products.Compound 9 was isolated and found to be enantiomerically pure by chiral NMR shift reagents.Compound 9 is formed by reaction of triplet diphenylcarbene with (S)-(+)-2-butanol to give a radical pair which subsequently collapses.The solid-state matrix directs the radical pair collapse with complete retention of configuration.
THE EFFECT OF OXYGEN ON THE MATRIX CHEMISTRY OF DIPHENYLCARBENE
Zayas, Jose,Platz, Matthew S.
, p. 2853 - 2856 (2007/10/02)
The effect of oxygen on the matrix chemistry of diphenylcarbene is described.
SINGLET-TRIPLET INTERCONVERSION OF DIPHENYLMETHYLENE. ENERGETICS, DYNAMICS AND REACTIVITIES OF DIFFERENT SPIN STATES
Eisenthal, K. B.,Turro, N. J.,Sitzmann, E. V.,Gould, I. R.,Hefferon, G.,et al.
, p. 1543 - 1554 (2007/10/02)
A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature.It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (1DPM and 3DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of kST and kTS allows determination of the equilibrium constant and change in free energy for the 1DPM*3DPM process.The absolute reactivity of 1DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.
