- Palladium-Catalyzed Reductive Aminocarbonylation of Benzylammonium Triflates with o-Nitrobenzaldehydes for the Synthesis of 3-Arylquinolin-2(1 H)-ones
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A palladium-catalyzed straightforward procedure for the synthesis of 3-arylquinolin-2(1H)-ones has been developed. The synthesis proceeds through a palladium-catalyzed reductive aminocarbonylation reaction of benzylic ammonium triflates with o-nitrobenzaldehydes, and a wide range of 3-arylquinolin-2(1H)-ones was obtained in moderate to good yields with very good functional group compatibility.
- Liu, Yongzhu,Qi, Xinxin,Wu, Xiao-Feng
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p. 13824 - 13832
(2021/10/12)
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- Base-Mediated Borylsilylation/Silylation of Ammonium Salts with Silylborane
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This work describes a base-mediated borylsilylation of benzylic ammonium salts to synthesize geminal silylboronates bearing benzylic proton under mild reaction conditions. Deaminative silylation of aryl ammonium salts was also achieved in the presence of
- Du, Xian,Guan, Yun-Shi,Li, Yi-Hui,Liang, Guohai,Luo, Yong,Qi, Wan-Ying,Wang, Zi-Ying,Wei, Xun,Xu, Xiao-Hong,Yuan, Han,Zhen, Jing-Song
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supporting information
p. 5988 - 5992
(2021/08/31)
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- Synthesis of Dibenzylic Diselenides from Elemental Selenium and Benzylic Quaternary Ammonium Salts
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Abstract: Substituted dibenzyl diselenides are synthesized in good yields (74–91 %) by SN2 nucleophilic substitution of benzylic trimethylammonium salts and diselenide dianion (Se2?), in situ generated from elemental selenium, under
- Chen, Feng,Li, Fuhai,Zeng, Qingle
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supporting information
p. 5605 - 5608
(2021/11/11)
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- Palladium-catalyzed phosphorylation of benzyl ammonium triflates with P(O)H compounds
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A palladium-catalyzed phosphorylation of benzyl ammonium triflates with P(O)H compounds has been developed. Various benzylphosphorus compounds were produced in good to excellent yields with high functional group tolerance. All the three kinds of hydrogen phosphoryl compounds, i.e. H-phosphonates, H-phosphinates and secondary phosphine oxides, were applicable to this reaction. The successful scale-up experiment and one-pot synthetic operation also well demonstrated its practicality.
- Chen, Tieqiao,Huang, Tianzeng,Liu, Long,Wang, Wenqi,Wang, Yuan,Xu, Hanshuang,Xu, Kaiqiang
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supporting information
(2020/03/03)
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- Cu2O-catalyzed C–S coupling of quaternary ammonium salts and sodium alkane-/arene-sulfinates
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A new protocol for the synthesis of (enantioenriched) benzylic sulfones via the Cu2O-catalyzed C–S bond cross coupling of alkane-/arene-sulfinates and (enantioenriched) benzylic quaternary ammonium salts has been developed. The product benzylic sulfones were obtained in good to high yields (75–96%). Chiral arylmethyl sulfones with high enantiomeric excess (90–94% ee) were also synthesized in the presence of Cu2O and 1,1′-bis-(diphenylphosphino)ferrocene (dppf).
- Chen, Hongyi,Huang, Youming,Zeng, Qingle,Zheng, Wenting
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supporting information
(2020/08/28)
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- Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
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A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
- Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
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supporting information
p. 13029 - 13032
(2020/11/07)
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- Palladium-Catalyzed C-N Cross-Coupling of NH-Heteroarenes and Quaternary Ammonium Salts via C-N Bond Cleavage
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In this paper, we extend the substrate class of Buchwald-Hartwig amination to quaternary ammonium salts. In the presence of Pd(OAc)2 and t-BuXPhos, the coupling of aryl- or arylmethyltrimethylammonium triflates with NH-heteroarenes via C-N bond cleavage affords the desired N-aryl or N-arylmethyl heteroarenes in moderate to excellent yields.
- Chen, Hongyi,Yang, Hongqin,Li, Nutao,Xue, Xinghua,He, Ze,Zeng, Qingle
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p. 1679 - 1685
(2019/08/20)
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- Palladium-catalyzed carbonylation of benzylic ammonium salts to amides and esters: Via C-N bond activation
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An efficient palladium-catalyzed carbonylation reaction of readily available quaternary ammonium salts with CO is reported for the first time to afford arylacetamides and arylacetic acid esters via benzylic C-N bond cleavage. This protocol features mild reaction conditions under atmospheric pressure of CO, a redox-neutral process without an additional oxidant, and a broad substrate scope for various kinds of amines, alcohols and phenols.
- Yu, Weijie,Yang, Shuwu,Xiong, Fei,Fan, Tianxiang,Feng, Yan,Huang, Yuanyuan,Fu, Junkai,Wang, Tao
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supporting information
p. 3099 - 3103
(2018/05/22)
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- Visible-Light-Driven External-Reductant-Free Cross-Electrophile Couplings of Tetraalkyl Ammonium Salts
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Cross-electrophile couplings between two electrophiles are powerful and economic methods to generate C-C bonds in the presence of stoichiometric external reductants. Herein, we report a novel strategy to realize the first external-reductant-free cross-electrophile coupling via visible-light photoredox catalysis. A variety of tetraalkyl ammonium salts, bearing primary, secondary, and tertiary C-N bonds, undergo selective couplings with aldehydes/ketone and CO2. Notably, the in situ generated byproduct, trimethylamine, is efficiently utilized as the electron donor. Moreover, this protocol exhibits mild reaction conditions, low catalyst loading, broad substrate scope, good functional group tolerance, and facile scalability. Mechanistic studies indicate that benzyl radicals and anions might be generated as the key intermediates via photocatalysis, providing a new direction for cross-electrophile couplings.
- Liao, Li-Li,Cao, Guang-Mei,Ye, Jian-Heng,Sun, Guo-Quan,Zhou, Wen-Jun,Gui, Yong-Yuan,Yan, Si-Shun,Shen, Guo,Yu, Da-Gang
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supporting information
p. 17338 - 17342
(2019/01/04)
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- Nickel-Catalyzed Borylation of Aryl- and Benzyltrimethylammonium Salts via C-N Bond Cleavage
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By developing a mild Ni-catalyzed system, a method for direct borylation of sp2 and sp3 C-N bonds has been established. The key to this hightly efficient C-N bond borylative cleavage depends on the appropriate choice of the nickel catalyst Ni(COD)2, ICy·HCl as a ligand, and the use of 2-ethoxyethanol as the cosolvent. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for gram-scale synthesis and late-stage C-N borylation of complex compounds.
- Hu, Jiefeng,Sun, Heqing,Cai, Wangshui,Pu, Xinghui,Zhang, Yemin,Shi, Zhuangzhi
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- Making Dimethylamino a Transformable Directing Group by Nickel-Catalyzed C-N Borylation
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The dimethylamino (Me2N) group is arguably the most versatile functional group capable of highly efficient and site-selective directed aromatic functionalizations at the ortho-, meta-, and para-positions depending on reaction conditions. While the repertoire of Me2N-directed reactions is growing at a rapid pace, the lack of a general method to transform this group to other functionalities hampers its wider application in organic synthesis. Here we report nickel-catalyzed C-N borylations of aryl- and benzyl-dimethylamines that permit the conversion of a huge library of largely underutilized Me2N-containing organic molecules into various functional molecules by taking advantage of the wealth of existing C-B functionalization methods.
- Zhang, Hua,Hagihara, Shinya,Itami, Kenichiro
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supporting information
p. 16796 - 16800
(2015/11/16)
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- Nickel-catalyzed cross couplings of benzylic ammonium salts and boronic acids: Stereospecific formation of diarylethanes via C-N bond activation
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We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts to diarylethanes with excellent chirality transfer, offering a new strategy for the synthesis of highly enantioenriched diarylethanes from readily available chiral benzylic amines.
- Maity, Prantik,Shacklady-Mcatee, Danielle M.,Yap, Glenn P. A.,Sirianni, Eric R.,Watson, Mary P.
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supporting information
p. 280 - 285
(2013/02/25)
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- Activation of acetonitrile in [Cp*Ir(η3-CH2CHCHPh)(NCMe)]+: Crystal structures of iridium-amidine, imino-ether, amido, and amide complexes
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Reactions of [Cp*Ir(η3-CH2CHCHPh)(NCMe)]OTf (1) with protic amines, alcohols, and water produce amidine complexes [Cp*Ir(η3-CH2CHCHPh)(NH=C(NR2)Me)]OTf (2) (R2 = (Me)2 (a), (Me)(H) (b), (i-Pr)(H) (c), (-CH2(CH2)3CH2-) (d)), imino-ether complexes [Cp*Ir-(η3-CH2CHCHPh)(NH=C(OR′)Me)]OTf (4) (R′ = Me (a), Et (b), i-Pr (c)), and amido complex Cp*Ir(η3-CH2CHCHPh)(NHC(=O)Me) (5-K), respectively. The keto form amido complex 5-K undergoes tautomerization to give the enol form complex Cp*Ir(η3-CH2CHCHPh)(N= C(OH)Me) (5-E) in polar solvents. Tertiary amines (NMe3, NEt3) react with 1 in chlorinated solvents (XCl) to give the chloro complex Cp*IrCl(η3-CH2CHCHPh) (3) and quaternary ammonium salts [R3NX]OTf(R = Me, Et and X = CH2Cl, CH3, CHCl2, CCl3, PhCH2). Crystal structures of 2a, 4a, 5-K, and [Cp*Ir(NH=C(OH)Me)(OH2)(PPh3)]OTf2 (6) have been determined by single-crystal X-ray diffraction analysis, which lead us to suggest hybrid structures, Ir--NH-C(=N+Me2)Me (2a′) for 2a and Ir--NH-C(=O+Me)Me (4a′) for 4a to some extent. Complexes 2 and 4 react with PPh3 to give an iridium(III) complex [Cp*Ir(η3-CH2CHCHPh)(PPh3)]OTf (7) and the free amidines NH=C(NR2)Me (8) and imino-ethers NH=C(OR′)Me (9), respectively. Nitrile complexes 1 and [Cp*Ir(η3-CH2CHCHPh)(NCCH= CHMe)]OTf(10) catalyze the hydration of the nitriles in the presence of Na2CO3 to produce amides, and the benzonitrile complex [Cp*Ir(η3-CH2CHCHPh)(NCPh)]OTf(11) catalyzes the methanolysis of benzonitrile in the presence of Na2CO3 to produce NH=C(OMe)Ph. Plausible mechanisms for these catalytic reactions are suggested with the amido and imino-ether complexes such as 4 and 5 being involved.
- Chin, Chong Shik,Chong, Daesung,Lee, Byeongno,Jeong, Hyunmok,Won, Gyongshik,Do, Youngkyu,Park, Young Ja
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p. 638 - 648
(2008/10/08)
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