6296-95-3Relevant articles and documents
Catalytic Reductive Cross-Coupling between Aromatic Aldehydes and Arylnitriles
Mitsui, Atsuhisa,Nagao, Kazunori,Ohmiya, Hirohisa
, p. 7094 - 7098 (2021/04/16)
A reductive cross-coupling reaction between aromatic aldehydes and arylnitriles using a copper catalyst and a silylboronate as a reductant is reported. This protocol represents an unprecedented approach to the chemoselective synthesis of α-hydroxy ketones by electrophile–electrophile cross-coupling.
Reductive coupling between aromatic aldehydes and ketones or imines by copper catalysis
Takeda, Mitsutaka,Mitsui, Atsuhisa,Nagao, Kazunori,Ohmiya, Hirohisa
supporting information, p. 3664 - 3669 (2019/02/14)
The copper-catalyzed reductive coupling of two different carbonyl compounds has been achieved. The reaction of aromatic aldehydes and arylketones with a silylboronate in the presence of a catalytic amount of a CuCl-N-heterocyclic carbene (NHC) complex and a stoichiometric amount of alkoxide base yielded cross-coupled 1,2-diol derivatives. A reaction pathway is proposed that involves the catalytic formation of a nucleophilic α-silyloxybenzylcopper(I) species from the aromatic aldehyde and its subsequent coupling with the arylketone. This process was amenable to asymmetric catalysis. This copper catalyst system also enabled the reductive coupling between aromatic aldehydes and imines.
Retropinacol/cross-pinacol coupling reactions - A catalytic access to 1,2-unsymmetrical diols
Scheffler, Ulf,Stoesser, Reinhard,Mahrwald, Rainer
supporting information, p. 2648 - 2652,5 (2012/12/12)
A new concept to access unsymmetrical 1,2-diols with high yields is reported. This new methodology is based on a retropinacol/cross-pinacol coupling process. This transformation is characterized by its operational simplicity and very mild reaction condi tions.
A one-pot cross-pinacol coupling/rearrangement procedure
Scheffler, Ulf,Mahrwald, Rainer
, p. 1970 - 1975,6 (2012/12/12)
A new catalytic retro-pinacol/cross-pinacol reaction, followed by subsequent rearrangement or deoxygenation of the intermediately formed vicinal diols, is described. This operationally simple one-pot protocol allows isolation of geminal α,α-diphenyl ketones or 1,1-diphenyl alkenes with high yields and selectivities. Copyright
Synthesis of unsymmetrical diolate, oxametallacyclopentene, amido-alkoxide and thiolato-alkoxide complexes using dialkyl and diaryl titanium aminotroponiminate complexes: A route to unsymmetrical vicinal diols
Steinhuebel, Dietrich P.,Lippard, Stephen J.
, p. 11762 - 11772 (2007/10/03)
The reactivity of [TiR2(Me2ATI)2] complexes, where Me2ATI = N,N′-dimethylaminotroponiminate, or L, with CO or RNC in the presence of various organic electrophiles has been investigated. The compounds TiMe2L2 and TiPh2L2 react with CO and aldehydes or ketones to afford unsymmetrical diolate complexes that convert to the corresponding vicinal diols after hydrolysis. Phenyl acetylene also reacts to form the oxametallacyclopentene complex [Ti(OCMe2CH=CPh)(Me2ATI)2]. Treatment of TiMe2L2 with RNC yields the free imine and a source of low-valent titanium. Trapping this intermediate with 2 equiv of benzaldehyde or benzil affords the titanium diolate or enediolate complex, respectively. When 1 equiv each of benzophenone and either N-tosylbenzaldimine or acetone were added to the intermediate, [Ti(Ph2COCN(SO2tol)HPh)(Me2-ATI)2] and [Ti(Ph2COCOMe2)(Me2ATI)2], respectively, were obtained. The titanium thiolato-alkoxide complex [Ti(Ph2CSCOMe2)(Me2ATI)2] was prepared by use of thiobenzophenone and acetone. This chemistry allows for the preparation of unsymmetrical diols and oxametallacyclopentene complexes from Ti(IV) dialkyls, CO, and either carbonyl compounds or alkynes. Amido-alkoxide and thiolato-alkoxide complexes can be prepared by the reaction of Ti(IV) dialkyl complex, 2 equiv of benzophenone, and either an imine or thioketone.
Electron Transfer in the Reactions of Aryllithium Compounds with Carbon Monoxide
Nudelman, N. Sbarbati,Doctorovich, Fabio
, p. 4651 - 4666 (2007/10/02)
The reactions of aryllithium compounds (Ar = phenyl, 1-naphthyl, xylyl, mesityl) with CO have been studied under several reaction conditions.A 13C NMR method developed to determine radicals at preparative concentrations revealed the presence of radical anions in the reaction mixtures in concentrations comparable to those of the reagents.ESR spectroscopic studies, the effect of radical inhibitors, kinetic measurements and isolation of derivatives of some intermediates suggest a mechanism that involves electron transfer as the first and rate determining step of the reaction.
C,O-dilithiated diarylmethanols: Easy and improved preparation by naphthalene-catalysed lithiation of diaryl ketones and reactivity toward electrophiles
Guijarro,Mancheno,Yus
, p. 1327 - 1334 (2007/10/02)
The lithiation of different diaryl ketones 1 with an excess of lithium powder and a catalytic amount (8 mol %) of naphthalene in tetradrofuran at -30°C leads to the formation of the corresponding dianions of the type I, with Met=Li, which react with several electrophiles (E+=MeI, EtBr, Pr(i)CHO, PhCHO, cyclohexanone, MeCN) to give, after hydrolysis, the expected substituted diarylmethanols 2.
Carbon Dioxide. A Reagent for the Protection of Nucleophilic Centers and the Simultaneous Activation for Electrophilic Attack. Part 4. The α-Substitution of (i) Benzyl Alcohol and (ii) Benzylamine
Katritzky, Alan R.,Fan, Wei-Qiang,Akutagawa, Kunihiko
, p. 415 - 418 (2007/10/02)
Benzyl alcohol is converted into a variety of α-substituted derivatives by a one-pot sequence involving lithiation of an intermediate hemicarbonate ester.Benzylamine is similarly converted by a one-pot sequence to α-substituted benzylamines: here an intermediate carbamate salt is involved.
