- Tert-Butoxide-Mediated Arylation of 2-Substituted Cyanoacetates with Diaryliodonium Salts
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A transition metal-free direct arylation of 2-substituted cyanoacetates with diaryliodonium salts was developed. With this approach, a wide range of α-tolunitrile derivatives has been synthesized in good to excellent yields of 45-92%. Furthermore, the practicability of this approach is further manifested in the synthesis of a related bioactive agent of glutarimide.
- Qian, Xiaofei,Han, Jianwei,Wang, Limin
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p. 940 - 946
(2016/04/05)
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- Cu(I)-catalyzed decarboxylative aldol-type and Mannich-type reactions for asymmetric construction of contiguous trisubstituted and quaternary stereocenters
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The catalytic asymmetric decarboxylative aldol-type reaction between aldehydes and cyanocarboxylic acids and Mannich-type reaction between aldimines and cyanocarboxylic acids were developed. α,α,β-Trisubstituted- β-hydroxy nitriles bearing contiguous all-carbon quaternary and trisubstituted stereocenters were produced with moderate enantio- and diastereoselectivity in the presence of 10 mol % CuOAc-TANIAPHOS (or DTBM-SEGPHOS) complex in the aldol-type reaction. α,α,β- Trisubstituted-β-amino nitriles containing contiguous all-carbon quaternary and trisubstituted stereocenters were produced with moderate to high enantio- and diastereoselectivity using 5 mol % CuOAc-(R)-DTBM-SEGPHOS complex in the Mannich-type reaction. These reactions proceed through Cu(I)-catalyzed decarboxylative nucleophile generation, followed by the addition of the resulting chiral Cu-ketenimide to aldehydes or imines. Because the reactions proceed under very mild conditions at nearly neutral pH, the reactions are applicable to a wide range of substrate combinations, including both aromatic and aliphatic substrates. Finally, α,α,β-trisubstituted-β- amino nitriles were converted to β2,2,3-amino acid derivatives through simple acidic hydrolysis without any racemization and epimerization.
- Yin, Liang,Kanai, Motomu,Shibasaki, Masakatsu
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scheme or table
p. 3497 - 3506
(2012/06/15)
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- Nucleophile generation via decarboxylation: Asymmetric construction of contiguous trisubstituted and quaternary stereocenters through a Cu(I)-catalyzed decarboxylative mannich-type reaction
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(Chemical Equation Presented) The first catalytic asymmetric decarboxylative Mannich-type reaction between aldimines and cyanocarboxylic acids was developed. α,α,β-Trisubstituted β-amino nitriles containing contiguous trisubstituted and all-carbon quatern
- Yin, Liang,Kanai, Motomu,Shibasaki, Masakatsu
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supporting information; experimental part
p. 9610 - 9611
(2011/03/19)
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- Palladium-catalyzed one-pot synthesis of 2-alkyl-2-arylcyanoacetates
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(Chemical Equation Presented) A one-pot procedure for the synthesis of 2-alkyl-2-arylcyanoacetates based on a Pd(OAc)2/DPPF (DPPF = 1,1′-diphenylphosphino ferreocene)-catalyzed enolate arylation followed by in situ alkylation has been developed. This procedure tolerates a diverse range of aryl and heteroaryl bromides, and provides a rapid entry to a variety of 2-alkyl-2-arylcyanoacetates in good to excellent yield.
- Wang, Xiang,Guram, Anil,Bunel, Emilio,Cao, Guo-Qiang,Allen, Jennifer R.,Faul, Margaret M.
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p. 1643 - 1645
(2008/09/17)
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- Selective Mono-methylation of Arylacetonitriles and Methyl Arylacetates by Dimethyl Carbonate
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Both arylacetonitriles and methyl arylacetates react with dimethyl carbonate (DMC) (20 molar excess) at 180 - 200 deg C in the presence of K2CO3 to produce monomethylated 2-arylpropionitriles and methyl 2-arylpropionates, respectively, with a selectivity >99.5percent.The reaction, with wide application, proceeds by DMC acting as a methoxycarbonylating agent towards the ArCH-X anion (X = CN, CO2Me) and as a methylating agent to ArC-(CO2Me)X.DMC also proved to be the best solvent for such reactions.
- Selva, Maurizio,Marques, Carlos Alberto,Tundo, Pietro
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p. 1323 - 1328
(2007/10/02)
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- SYNTHESIS OF FLUORINATED DERIVATIVES OF GLUTETHIMIDE AND AMINOGLUTETHIMIDE
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Aminoglutethimide (1), used in the treatment of hormone dependent breast cancer, interacts with enzyme complexes desmolase and aromatase.Its action is not specific and its metabolism gives rise to toxic and non-inhibitory metabolites.The work described here explores the impact of fluorine substitution within the glutethimide (2) framework, on the enzyme inhibitory properties of aminoglutethimide.Four new fluorinated derivatives (5), (6), (8) and (9) have been prepared, in which fluorine substituents have been introduced into the phenyl ring and the ethyl side chain. 4-Fluoroglutethimide (5) and 3-trifluoroglutethimide (6) were synthesised from the corresponding fluorophenylacetonitriles (10) and (14) via sequential monoethylation, Michael addition to methyl propenoate and cyclisation.An alternative strategy, devised for the synthesis of (8), involved the monoarylation of ethyl cyanoacetate, and gave rise to the intermediate (29).Incorporation of fluorine was carried out by SF4 fluorination of the cyanoketoester (33), which was subsequently converted to the difluoroaminoglutethimide (8).For the synthesis of trifluoromethyl glutethimide (9), the trifluoromethyl group was introduced by alkylation of phenylcyanoacetate (16) with 2-iodo-1,1,1-trifluoroethane.Preliminary in vitro enzyme inhibition results have been obtained for compounds (5), (6) and (8).
- Hammond, Gerald B.,Plevey, Raymond G.,Sampson, Paul,Tatlow, John Colin
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- Reactions of Triphenylphosphine- and Trialkyl Phosphite-Silver Nitrate Complexes with Positive Halogen Compounds. Synthesis of α-Nitro Nitriles
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The reaction of α-bromo-α-cyano esters, α-bromo-α-cyano nitriles, and α-bromo-α-cyano imides with triphenylphosphine- or trialkyl phosphite-silver nitrate complexes leads to replacement of the positive bromine atom by a nitro group under mild conditions.I
- Ketari, Rachid,Foucaud, Andre
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p. 4498 - 4501
(2007/10/02)
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