10527-66-9Relevant academic research and scientific papers
Mannich-like three-component synthesis of α-branched amines involving organozinc compounds: ReactIR monitoring and mechanistic aspects
Le Gall, Erwan,Sengmany, Stéphane,Hauréna, Caroline,Léonel, Eric,Martens, Thierry
, p. 27 - 35 (2013)
The infra-red spectroscopic in situ examination of the Mannich-like three-component reaction between organozinc reagents, amines and aldehydes is described, revealing that two distinct pathways are favored, depending on the nature of the starting amine. While reactions involving primary amines proceed via in situ-formed imines, reactions involving secondary amines rather imply a hemiaminal as the key intermediate species.
A four-component reaction involving in situ generated organometallic reagents: Straightforward access to β-amino esters
LeGall, Erwan,Leonel, Eric
, p. 5238 - 5241 (2013)
Four in one: A straightforward synthesis of β2,3-amino esters is described through a new zinc-mediated, cobalt-catalyzed four-component reaction between organic bromides, alkyl acrylates, amines, and aldehydes (see scheme). Synthesis involves a Mannich-related conjugate addition/aza-aldol domino sequence, allowing the formation of three single bonds in one step. A reaction mechanism, emphasizing the crucial role of zinc salts, is described. Copyright
Atom-efficient transition-metal-free arylation ofN,O-acetals using diarylzinc reagents through Zn/Zn cooperativity
Borys, Andryj M.,Gil-Negrete, Jose M.,Hevia, Eva
supporting information, p. 8905 - 8908 (2021/09/10)
Exploiting the cooperative action of Lewis acid Zn(C6F5)2with diarylzinc reagents, the efficient arylation ofN,O-acetals to access diarylmethylamines is reported. Reactions take place under mild reaction conditions without the need for transtion-metal catalysis. Mechanistic investigations have revealed that Zn(C6F5)2not only acts as a Lewis acid activator, but also enables the regeneration of nucleophilic ZnAr2species, allowing a limiting 50 mol% to be employed.
Metal-free iodine-promoted direct synthesis of unsymmetrical triarylmethanes
Gu, Ying-Chun,Huang, Jie,Wu, Run-Shi,Xu, Da-Zhen,Yang, Qi,Yu, Ya-Qin
, p. 5519 - 5525 (2020/04/17)
A highly efficient strategy to synthesize completely unsymmetrical triarylmethanes promoted by iodine under metal-free conditions has been successfully developed. Three different aryl groups were introduced into triarylmethanes in a one-pot reaction from inexpensive and readily available salicylaldehydes, arylboronic acids and arenes via o-QM intermediates generated in situ, delivering a wide range of unsymmetrical triarylmethanes bearing various functional groups in good yields with excellent chemoselectivity.
Copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals under atmosphere leading to α-aryl glycine derivatives and diarylmethylamine derivatives
Sakai, Norio,Hori, Hiroaki,Yoshida, Yoshihiro,Konakahara, Takeo,Ogiwara, Yohei
, p. 4722 - 4729 (2015/07/27)
We demonstrated a copper(I)-catalyzed coupling reaction of aryl boronic acids with N,O-acetals and N,N-aminals leading to the synthesis of α-aryl glycines and diarylmethylamines. Under an ambient atmosphere, this catalytic system could be applied to the activation of a C(sp3)-O bond of N,O-acetals with an ester and an aryl group, or without a coordinating substituent, as well as to a C(sp3)-N bond of N,N-aminals.
Can one predict changes from SN1 to SN2 mechanisms?
Thanh, Binh Phan,Nolte, Christoph,Kobayashi, Shinjiro,Ofial, Armin R.,Mayr, Herbert
supporting information; experimental part, p. 11392 - 11401 (2011/02/27)
The reactions of substituted benzhydryl bromides Ar2CHBr with primary and secondary amines in DMSO yield benzhydryl amines Ar 2CHNRR′, benzophenones Ar2CdO, and benzhydrols Ar2CHOH. Kinetic investigations at 20°C revealed the rate law -d[Ar2CHBr]/dt = (k1 + k2[HNRR′])[Ar 2CHBr], where the amine independent term k1 gave rise to the formation of Ar2CdO and Ar2CHOH and the amine-dependent term k2[HNRR′] was responsible for the formation of Ar2CHNRR′. Clear evidence for concomitant S N1 and SN2 processes was obtained. While the rate constants of the SN1 reactions correlate with Hammett's σ+ constants (ρ = -3.22), the second-order rate constants k2 for the SN2 reactions are not correlated with the electron releasing abilities of the substituents, indicating that the transition states of the SN2 reactions do not merge with the transition states of the SN1 reactions. The correlation equation log k 20°C = s(E + N), where nucleophiles are characterized by N and s and electrophiles are characterized by E (J. Am. Chem. Soc. 2001, 123, 9500-9512), was used to calculate the lifetimes of benzhydrylium ions in the presence of amines and DMSO. The change from SN1 to SN2 mechanism occurred close to the point where the calculated rate constant for the collapse of the benzhydrylium ions with the amines just reaches the vibrational limit; that is, the concerted SN2 mechanism was only followed when it was enforced by the lifetime of the intermediate. The nucleophile-specific parameters N and s needed for this analysis were determined by studying the kinetics of the reactions of a variety of amines with amino-substituted benzhydrylium tetrafluoroborates (Ar2CH+BF4-) of known electrophilicity E in DMSO. Analogously, the rates of the reactions of laser flash photolytically generated benzhydrylium ions Ar2CH + with DMSO in acetonitrile were employed to determine the nucleophile-specific parameters N and s of DMSO, and it is reported that DMSO is a significantly stronger O-nucleophile than water and ordinary alcohols.
Synthesis of tertiary sec-alkylamines by the addition of grignard reagents to N,N-dialkylformamides mediated by Ti(OiPr)4 and Me3SiCl
Tomashenko, Olesya,Sokolov, Viktor,Tomashevskiy, Alexander,Buchholz, Herwig A.,Welz-Biermann, Urs,Chaplinski, Vladimir,De Meijere, Armin
experimental part, p. 5107 - 5111 (2009/06/17)
A number of tertiary sec-alkylamines (22 examples, 29-80% yield) have been prepared according to a simple one-pot procedure by the addition of Grignard reagents to N,N-dialkylformamides in the presence of Ti(OiPr)4 and Me3SiCl. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
