- Palladium-Catalyzed Cross-Coupling of Superbase-Generated C(sp3) Nucleophiles
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A range of methods has been investigated recently for the arylation of weakly acidic C(sp3)-H bonds, primarily exploiting directed metalation with a transition metal catalyst or radical formation via hydrogen atom transfer. In this work, a classical base-mediated approach is taken, exploiting the ability of organometallic superbases to metalate very weakly acidic (pKa> 40) C-H bonds. Conditions are developed with eithern-BuLi/diamine orn-BuLi/KOtBu superbases to enable metalation to occur with high selectivity. Organolithium nucleophiles can be directly used in cross-coupling, or organozincs can be formed to enable reactions with functional group-dense organohalides.
- Freure, Garrett P. R.,Lavertu, Jean-Danick E.,Newman, Stephen G.,Skrotzki, Eric A.
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p. 12258 - 12263
(2021/10/26)
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- Substituted Hantzsch Esters as Versatile Radical Reservoirs in Photoredox Reactions
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Substituted Hantzsch esters can act as radical reservoirs in photoredox reactions, steadily releasing a carbon radical and a hydrogen atom radical in the absence of an additional electron acceptor. We propose that radical release by substituted Hantzsch esters occurs via a mechanism involving an internal redox cycle. Cinnamidecinnamides, styrenes, α,β-unsaturated acids, and diarylethenes could be alkylated smoothly with these reagents. (Figure presented.).
- Gu, Fangjun,Huang, Wenhao,Liu, Xu,Chen, Wenxin,Cheng, Xu
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supporting information
p. 925 - 931
(2018/01/04)
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- Construction of 3-arylpropylamines using Heck arylations. the total synthesis of cinacalcet hydrochloride, alverine, and tolpropamine
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New synthetic routes toward the commercial drugs cinacalcet hydrochloride, alverine, and tolpropamine were developed using a Heck-Matsuda arylation as the key-step. Several reaction conditions were evaluated for the Heck-Matsuda reaction using allylamine derivatives and arenediazonium salts. For cinacalcet hydrochloride, N-formylamide provided the best result, furnishing the synthetic target in a very high overall yield (75% over five steps). For alverine, the best results were obtained using a double Heck-Matsuda strategy, providing alverine in an excellent overall yield (69%) from N-acetyl diallylamine in three steps. Tolpropamine was synthesized in a 46% yield over five steps using an efficient reductive Heck-Matsuda arylation between p-bromo-methylcinnamate with 3-chloro tolyldiazonium salt, generating the ,diaryl propionate that was converted to tolpropamine.
- Prediger, Patrícia,Da Silva, Allan Ribeiro,Correia, Carlos Roque Duarte
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p. 3333 - 3341
(2014/05/06)
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- Hydroaminomethylation with novel Rhodium-Carbene complexes: An efficient catalytic approach to pharmaceuticals
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Starting from [{Rh(cod)Cl}2] and 1,3-dimesitylimidazole-2- ylidenes the novel [RhCl(cod)(carbene)] complexes 1-5 have been synthesized, characterized, and tested in the hydroaminomethylation of aromatic olefins. The influence of different ligands and reaction parameters on the catalytic activity was investigated in detail applying 1,1-diphenylethylene and piperidine as a model system. The scope and limitations of the novel catalysts is shown in the preparation of 16 biologically active 1-amino-3,3-diarylpropenes. In general, high chemo- and regioselectivity as well as good yields of the desired products were achieved.
- Ahmed, Moballigh,Buch, Cathleen,Routaboul, Lucie,Jackstell, Ralf,Klein, Holger,Spannenberg, Anke,Beller, Matthias
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p. 1594 - 1601
(2008/02/04)
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- Simple synthetic equivalents for the β-(N,N-disubstituted)ethylamino acyl cation synthon and their applications
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Various N,N-disubstituted-β-amino-N-methoxy-N-methylpropanamides 3a-i were prepared which served as an excellent β-aminoacyl cation equivalents. These were used to prepare β-amino ketones 1, pharmacologically active tertiary 1-(3,3-diarylpropyl)amines 7a-c, and the interesting C-glycoside 8.
- Selvamurugan,Aidhen
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p. 2239 - 2246
(2007/10/03)
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- One-pot synthesis of pharmacologically active secondary and tertiary 1- (3,3-diarylpropyl)amines via rhodium-catalysed hydroaminomethylation of 1,1- diarylethenes
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Pharmacologically active secondary and tertiary 1-(3,3- diarylpropyl)amines 1 are prepared in high yields and chemoselectivity by the reaction of 1,1-diarylethenes 4, primary or secondary amines 5, carbon monoxide and hydrogen in presence of [Rh(cod)Cl]2/PBu3 as catalyst via a one-pot hydroformylation - amine condensation - reduction sequence.
- Rische, Thorsten,Eilbracht, Peter
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p. 1915 - 1920
(2007/10/03)
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- Reductive electrophilic substitution of diarylmethyl methyl ethers: Synthetic applications
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The reductive cleavage of diarylmethyl methyl ethers with Li metal in THF led to quantitative formation of the corresponding diarylmethyl anions. Quenching with electrophiles afforded substituted diarylmethanes in good to excellent yields.
- Azzena,Melloni,Fenude,Fina,Marchetti,Sechi
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p. 591 - 599
(2007/10/02)
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