37746-17-1Relevant articles and documents
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Miller,R.G. et al.
, p. 4211 - 4220 (1974)
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Enantioselective Synthesis of N-Alkylamines through β-Amino C-H Functionalization Promoted by Cooperative Actions of B(C6F5)3and a Chiral Lewis Acid Co-Catalyst
Chang, Yejin,Cao, Min,Chan, Jessica Z.,Zhao, Cunyuan,Wang, Yuankai,Yang, Rose,Wasa, Masayuki
supporting information, p. 2441 - 2455 (2021/02/16)
We disclose a catalytic method for β-C(sp3)-H functionalization of N-alkylamines for the synthesis of enantiomerically enriched β-substituted amines, entities prevalent in pharmaceutical compounds and used to generate different families of chiral catalysts. We demonstrate that a catalyst system comprising of seemingly competitive Lewis acids, B(C6F5)3, and a chiral Mg- or Sc-based complex, promotes the highly enantioselective union of N-alkylamines and α,β-unsaturated compounds. An array of δ-amino carbonyl compounds was synthesized under redox-neutral conditions by enantioselective reaction of a N-alkylamine-derived enamine and an electrophile activated by the chiral Lewis acid co-catalyst. The utility of the approach is highlighted by late-stage β-C-H functionalization of bioactive amines. Investigations in regard to the mechanistic nuances of the catalytic processes are described.
Iron-catalyzed oxidative C(3)-H functionalization of amines
Takasu, Noriaki,Oisaki, Kounosuke,Kanai, Motomu
, p. 1918 - 1921 (2013/06/04)
Fe-catalyzed direct dehydrogenative C(3)-functionalization of tertiary arylamines was developed via activation of the sp3 C(3)-H bond. The reaction is applicable to both cyclic and acyclic amines. The key process is the catalytic desaturative enamine formation from tertiary amines and position-selective C-C bond formation (addition to nitro olefins) at the β-carbon. Products can be converted to versatile and unique nitrogen-containing molecules.
Intramolecular and Intermolecular Reactions of Alkenylsilyl Radicals
Chatgilialoglu, Chryssostomos,Woynar, Helmut,Ingold, Keith U.
, p. 555 - 562 (2007/10/02)
The radicals formed during photolysis of di-t-butyl peroxide and a number of alkenyldimethylsilanes have been examined by e.s.r. spectroscopy.Only carbon-centred radicals were observed.These were either secondary alkyl radicals formed by the addition of the initially formed silyl radical to a double bond and/or allyl radicals formed by hydrogen-atom abstraction from the alkenyl group.In most cases addition to the double bond was an intermolecular process.However, pent-4-enylsilyl radicals undergo intramolecular addition with endo-cyclization to form the six-membered ring being strongly favoured over exo-cyclization to form the five-membered ring.This preference was confirmed by product studies on 3,3-dimethylpent-4-enyldimethylsilane.The factors that control homolytic exo:endo cyclization rates for species in which the radical centre is located on a second row element are adumbrated.