1181394-16-0Relevant articles and documents
One-Pot Synthesis of Primary and Secondary Aliphatic Amines via Mild and Selective sp3 C?H Imination
Comito, Robert J.,Ghosh, Subrata K.,Hu, Mengnan
supporting information, p. 17601 - 17608 (2021/11/03)
The direct replacement of sp3 C?H bonds with simple amine units (?NH2) remains synthetically challenging, although primary aliphatic amines are ubiquitous in medicinal chemistry and natural product synthesis. We report a mild and selective protocol for preparing primary and secondary aliphatic amines in a single pot, based on intermolecular sp3 C?H imination. The first C?H imination of diverse alkanes, this method shows useful site-selectivity within substrates bearing multiple sp3 C?H bonds. Furthermore, this reaction tolerates polar functional groups relevant for complex molecule synthesis, highlighted in the synthesis of amine pharmaceuticals and amination of natural products. We characterize a unique C?H imination mechanism based on radical rebound to an iminyl radical, supported by kinetic isotope effects, stereoablation, resubmission, and computational modeling. This work constitutes a selective method for complex amine synthesis and a new mechanistic platform for C?H amination.
Enantioselective, iridium-catalyzed monoallylation of ammonia
Pouy, Mark J.,Stanley, Levi M.,Hartwig, John F.
supporting information; experimental part, p. 11312 - 11313 (2011/03/19)
(Chemical Equation Presented) Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and di
Salt-free iridium-catalyzed asymmetric allylic animations with N,N-diacylamines and ortho-nosylamide as ammonia equivalents
Weihofen, Robert,Tverskoy, Olena,Helmchen, Guenter
, p. 5546 - 5549 (2007/10/03)
(Chemical Equation Presented) New variants of the iridium-catalyzed allylic substitution allow N-protected and non-protected chiral allylamines to be prepared with high enantio- and regio-selectivity. The allylamines are used as nucleophiles in highly dia
Synthesis of pharmacologically relevant indoles with amine side chains via tandem hydroformylation/fischer indole synthesis
Schmidt, Axel M.,Eilbracht, Peter
, p. 5528 - 5535 (2007/10/03)
The sequence of hydroformylation and Fischer indole synthesis starting from amino olefins and aryl hydrazines is described. In a convergent manner, the two units bearing pharmacologically relevant substituents are assembled in the final indolization step. This modular and diversity-oriented approach to tryptamines and homotryptamines can be conducted in water and allows synthesis of branched and nonbranched tryptamines as well as tryptamine-based pharmaceuticals such as the 5-HT1D agonist L 775 606.
Asymmetric synthesis of chiral amines by highly diastereoselective 1,2- additions of organometallic reagents to N-tert-butanesulfinyl imines
Cogan, Derek A.,Liu, Guangcheng,Ellman, Jonathan
, p. 8883 - 8904 (2007/10/03)
High yielding and highly diastereoselective methods for 1,2-additions of organometallic reagents to N-tert-butanesulfinyl aldimines (2) and N-tert- butanesulfinyl kerimines (3) are described. The additions of alkyl, aryl, alkenyl, and allyl carbanions to a diverse set of imines with different steric and electronic properties are demonstrated. Acidic methanolysis of the sulfinamide products (4 and 6) delivers highly enantioenriched α-branched and α,α-dibranched amines. Since a broad range of sulfinyl imines are easily accessible from aldehydes and ketones, a wide variety of enantioentriched amines may be prepared.
