Synthesis and properties of symm-triazines. 3. Reactions of 2-alkyl-4,6-bistrichloromethyl-symm-triazines containing higher alkyl groups with ammonia and aliphatic amines

1985 ◽  
Vol 21 (11) ◽  
pp. 1284-1289 ◽  
Author(s):  
V. I. Kelarev ◽  
Ammar Dibi ◽  
A. F. Lunin
Keyword(s):  
Aliphatic Amines ◽  
Alkyl Groups

Formation of Radical Intermediates in Sulphur Dioxide Solutions of Tertiary Aliphatic Amines

1974 ◽  
Vol 29 (11-12) ◽  
pp. 742-749 ◽  
Author(s):  
M. H. Donbavand ◽  
H. J. Möckel
Keyword(s):  
Sulphur Dioxide ◽  
Free Radical Oxidation ◽  
Molecular Iodine ◽  
Coupling Constants ◽  
Aliphatic Amines ◽  
Stable Free Radical ◽  
Radical Oxidation ◽  
Radical Intermediates ◽  
Alkyl Groups ◽  
Liquid Sulphur

The addition of molecular iodine to solutions of tertiary aliphatic amines in liquid sulphur dioxide is found to result in the formation of stable free radical oxidation intermediates. In triethylamine solutions, oxidised under these conditions, aromatisation appears to take place to produce a pyridinyl radical. Radicals formed from N-ethyldimethylamine, Ν,Ν-diethylmethylamine and tri-n-propylamine on the other hand appear to be essentially aliphatic in character, with two of the N-alkyl groups intact. The magnitude of the measured coupling constants however, implies some delocalisation in the “damaged” alkyl group, possibly via a tautomeric mechanism. A number of mechanistic possibilities are explored to account for the roles played by iodine and sulphur dioxide in these reactions.

scholarly journals Enantioselective Access to Dialkyl Amines and Alcohols via Ni-Catalyzed Reductive Hydroalkylations

2021 ◽  
Author(s):  
Shan Wang ◽  
Tian-Yi Zhang ◽  
Jian-Xin Zhang ◽  
Huan Meng ◽  
Bi-Hong Chen ◽  
...  
Keyword(s):  
Natural Products ◽  
Functional Group ◽  
Alkyl Halides ◽  
Aliphatic Amines ◽  
Fine Chemicals ◽  
Alkyl Groups ◽  
Simple Protocol ◽  
Enol Esters

Abstract Chiral dialkyl amines and alcohols are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective reductive hydroalkylation of acyl enamines and enol esters with alkyl halides to afford enantioenriched α-branched aliphatic amines and alcohols in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral dialkyl amine and alcohol derivatives from simple starting materials with great functional group tolerance.

scholarly journals Enantioselective Access to Dialkyl Amines and Alcohols via Ni-Catalyzed Reductive Hydroalkylations

2020 ◽  
Author(s):  
Shan Wang ◽  
Tian-Yi Zhang ◽  
Jian-Xin Zhang ◽  
Huan Meng ◽  
Bi-Hong Chen
Keyword(s):  
Natural Products ◽  
Functional Group ◽  
Alkyl Halides ◽  
Aliphatic Amines ◽  
Fine Chemicals ◽  
Alkyl Groups ◽  
Simple Protocol

Chiral dialkyl amines and alcohols are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective reductive hydroalkylation of enamides and enolates with alkyl halides to afford enantioenriched α-branched aliphatic amines and alcohols in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral dialkyl amine and alcohol derivatives from simple starting materials with great functional group tolerance.

Electron Spin Resonance Studies of the Radiolysis of Aliphatic Amines at 77 °K

1971 ◽  
Vol 49 (11) ◽  
pp. 1869-1879 ◽  
Author(s):  
P. Wardman ◽  
D. R. Smith
Keyword(s):  
Electron Spin Resonance ◽  
Electron Spin ◽  
Aliphatic Amines ◽  
Methyl Ethyl ◽  
Alkyl Radicals ◽  
Restricted Rotation ◽  
Parallel Component ◽  
Alkyl Groups ◽  
Spin Resonance ◽  
Butyl Amine

Several frozen aliphatic amines have been γ-irradiated at 77 °K and the electron spin resonance (e.s.r.) spectra of the trapped radicals obtained at 77 °K and on warming. Radiolysis of methyl, ethyl and isopropyl amines produces predominantly alkylamino [Formula: see text] radicals. The proton hyperfine (h.f.) couplings of [Formula: see text] radicals are 10–30% larger than those in the corresponding isoelectronic alkyl radicals and the parallel component of the 14N coupling is about 35 G. Restricted rotation of alkyl groups occurs at 77 °K in some cases. On warming from 77 °K, the [Formula: see text] radicals generally abstract from the solvent or isomerize to produce radicals of the aminoalkyl type (e.g. RĊHNH2). The alkyl proton h.f. splittings of these latter radicals are 20–40% lower than in the corresponding alkyl radicals, and the observed 14N coupling was [Formula: see text] in ĊH2NR2 and [Formula: see text] in (CH3)2ĊNH2 and CH3ĊHNH2. The amino proton couplings in the aminoalkyl radicals were not resolved. Irradiated dimethylamine produces both (CH3)2N and CH2N(CH3) radicals, but (CH3)2N disappears on warming. Only ĊH2N(CH3)2 was observed after irradiation of (CH3)3N at 77 °K. Solid methoxyamine (giving CH3ONH) and tert-butyl-amine were also studied.

scholarly journals Enantioselective access to chiral aliphatic amines and alcohols via Ni-catalyzed hydroalkylations

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Shan Wang ◽  
Jian-Xin Zhang ◽  
Tian-Yi Zhang ◽  
Huan Meng ◽  
Bi-Hong Chen ◽  
...  
Keyword(s):  
Natural Products ◽  
Functional Group ◽  
Aliphatic Amine ◽  
Alkyl Halides ◽  
Aliphatic Amines ◽  
Fine Chemicals ◽  
Alkyl Groups ◽  
Simple Protocol ◽  
Enol Esters

AbstractChiral aliphatic amine and alcohol derivatives are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective hydroalkylation of acyl enamines and enol esters with alkyl halides to afford enantioenriched α-branched aliphatic acyl amines and esters in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral secondary alkyl-substituted amine and secondary alkyl-substituted alcohol derivatives from simple starting materials with great functional group tolerance.

scholarly journals Enantioselective Access to Dialkyl Amines and Alcohols via Ni-Catalyzed Reductive Hydroalkylations

2020 ◽  
Author(s):  
Shan Wang ◽  
Tian-Yi Zhang ◽  
Jian-Xin Zhang ◽  
Huan Meng ◽  
Bi-Hong Chen
Keyword(s):  
Natural Products ◽  
Functional Group ◽  
Alkyl Halides ◽  
Aliphatic Amines ◽  
Fine Chemicals ◽  
Alkyl Groups ◽  
Simple Protocol

Chiral dialkyl amines and alcohols are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective reductive hydroalkylation of enamides and enolates with alkyl halides to afford enantioenriched α-branched aliphatic amines and alcohols in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral dialkyl amine and alcohol derivatives from simple starting materials with great functional group tolerance.

scholarly journals Enantioselective Access to Dialkyl Amines and Alcohols via Ni-Catalyzed Reductive Hydroalkylations

2021 ◽  
Author(s):  
Shan Wang ◽  
Tian-Yi Zhang ◽  
Jian-Xin Zhang ◽  
Huan Meng ◽  
Bi-Hong Chen
Keyword(s):  
Natural Products ◽  
Functional Group ◽  
Alkyl Halides ◽  
Aliphatic Amines ◽  
Fine Chemicals ◽  
Alkyl Groups ◽  
Simple Protocol

Chiral dialkyl amines and alcohols are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective reductive hydroalkylation of enamides and enolates with alkyl halides to afford enantioenriched α-branched aliphatic amines and alcohols in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral dialkyl amine and alcohol derivatives from simple starting materials with great functional group tolerance.

Exogenous Directing Group Free, Ligand-Enabled gamma-C(sp3)–H Arylation of Free Primary Aliphatic Amines and α-Amino Esters

2019 ◽  
Author(s):  
Yongzheng Ding ◽  
Shuai Fan ◽  
Xiaoxi Chen ◽  
yuzhen gao ◽  
Gang Li
Keyword(s):  
Amino Acids ◽  
Large Scale ◽  
Free Ligand ◽  
Aliphatic Amines ◽  
Rapid Synthesis ◽  
Amino Esters ◽  
Directing Group ◽  
Large Scale Synthesis ◽  
Primary Aliphatic Amines

A Pdᴵᴵ-catalyzed, ligand-enabled gamma-C(sp3)–H arylation of free primary aliphatic amines and amino esters without using an exogenous directing group is reported. This reaction is compatible with unhindered free aliphatic amines, and it is also be applicable to the rapid synthesis of biologically and synthetically valuable unnatural α-amino acids. Large scale synthesis is also feasible using this method.<br>

Sign in / Sign up

Export Citation Format

Share Document