- N-Heterocyclic Carbene-Catalyzed Decarboxylative Alkylation of Aldehydes
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We found that N-heterocyclic carbene catalysis promoted the unprecedented decarboxylative coupling of aryl aldehydes and tertiary or secondary alkyl carboxylic acid-derived redox-active esters to produce aryl alkyl ketones. The mild and transition-metal-free reaction conditions are attractive features of this method. The power of this protocol was demonstrated by the functionalization of pharmaceutical drugs and natural product. A reaction pathway involving single electron transfer from an enolate form of Breslow intermediate to a redox ester followed by recombination of the resultant radical pair to form a carbon-carbon bond is proposed.
- Ishii, Takuya,Kakeno, Yuki,Nagao, Kazunori,Ohmiya, Hirohisa
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supporting information
p. 3854 - 3858
(2019/04/25)
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- Enantioselective hydrogenation and transfer hydrogenation of bulky ketones catalysed by a ruthenium complex of a chiral tridentate ligand
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A study on the enantioselective hydrogenation of tertiary alkyl ketones catalysed by a novel class of tridentate-Ru complex is reported. In contrast to the extensively studied [RuCl2(diphos)(di-primary amine)] complexes, this new class of hydro
- Diaz-Valenzuela, M. Belen,Phillips, Scott D.,France, Marcia B.,Gunn, Mary E.,Clarke, Matthew L.
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supporting information; experimental part
p. 1227 - 1232
(2009/08/10)
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- Direct formation of secondary and tertiary alkylzinc bromides and subsequent Cu(I)-mediated couplings
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Secondary and tertiary alkylzinc bromides can be generated from the direct oxidative addition of Rieke zinc to secondary and tertiary alkyl bromides in high yield. These organozinc reagents have been found to undergo copper-catalyzed conjugate addition, cross-coupling with acid chlorides, and carbocupration to activated alkynes.
- Rieke, Reuben D.,Hanson, Mark V.,Brown, Jeffrey D.,Niu, Q. Jason
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p. 2726 - 2730
(2007/10/03)
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- Direct formation of secondary and tertiary alkylzinc bromides
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The direct formation of secondary and tertiary alkylzinc bromides can be accomplished under mild conditions from the direct oxidative addition of Rieke zinc to secondary and tertiary alkyl bromides including remote functionalized halides.
- Hanson, Mark V.
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p. 7205 - 7208
(2007/10/02)
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- Rearrangement of Ketones. Part 4. Aluminium Chloride Catalysed Rearrangement of Some 2,2-Dialkyl-1-phenyl-1-propan-1-ones
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Four α,α,α-trisubstituted acetophenones ((1):R1=R2=R3=CH3; (2):R1=R2=CH3, R3=CH2CH3; (3):R1=R2=CH3, R3=CH2Ph; (4):R1=CH3, R2=CH2CH3, R3=CH2Ph) were prepared.Ketones (1)-(4) were treated with aluminium chloride to induce rearrangement to alkyl ketones.The phenyl ketones behaved as follows: (1) gave 3-methyl-3-phenylbutan-2-one (7), (2) gave 3-methyl-3-phenylpentan-2-one (8) and 2-methyl-2-phenylpentan-3-one (9), (3) gave 3-methyl-3,4-diphenylbutan-2-one (10) and 3-methyl-1,3-diphenylbutan-2-one (11), and (4) gave 3-methyl-1,3-diphenylpentan-2-one (12), 2-methyl-1,2-diphenylpentan-3-one (13) and 3-benzyl-3-phenylpentan-2-one (14).A tentative mechanism for the rearrangement is proposed.
- Fernandez-Monreal, Maria C.,Ruiz, Maria P.
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p. 440 - 472
(2007/10/02)
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