115270-11-6Relevant articles and documents
N-Methyl Allylic Amines from Allylic Alcohols by Mitsunobu Substitution Using N-Boc Ethyl Oxamate
Van Veen, Branca C.,Wales, Steven M.,Clayden, Jonathan
, p. 8538 - 8543 (2021/06/30)
We report the practical, scalable synthesis of a range of N-methyl allylic amines. Primary and secondary allylic alcohols underwent a regioselective Mitsunobu reaction with readily accessible N-Boc ethyl oxamate to deliver the corresponding N-Boc allylic amines, including in enantiopure form via stereospecific substitution. Subsequent N-methylation and Boc deprotection without chromatography yielded the amine products as hydrochloride salts. This method solves the problem of converting commercially available alcohols into often volatile N-methyl allylic amines, many of which have limited commercial availability.
Direct β-Selective Hydrocarboxylation of Styrenes with CO2 Enabled by Continuous Flow Photoredox Catalysis
Seo, Hyowon,Liu, Aofei,Jamison, Timothy F.
supporting information, p. 13969 - 13972 (2017/10/17)
The direct β-selective hydrocarboxylation of styrenes under atmospheric pressure of CO2 has been developed using photoredox catalysis in continuous flow. The scope of this methodology was demonstrated with a range of functionalized terminal styrenes, as well as α-substituted and β-substituted styrenes.
Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of trans-1,2-Disubstituted Alkenes
Chen, Caiyou,Jin, Shicheng,Zhang, Zhefan,Wei, Biao,Wang, Heng,Zhang, Kai,Lv, Hui,Dong, Xiu-Qin,Zhang, Xumu
, p. 9017 - 9020 (2016/08/05)
The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging trans-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility of our method. A creative route for the synthesis of vernakalant and Enablex was also developed.
Platinum-catalyzed direct amination of allylic alcohols with aqueous ammonia: Selective synthesis of primary allylamines
Das, Kalpataru,Shibuya, Ryozo,Nakahara, Yasuhito,Germain, Nicolas,Ohshima, Takashi,Mashima, Kazushi
supporting information; experimental part, p. 150 - 154 (2012/02/16)
Direct amination of unactivated allylic alcohols with aqueous ammonia was catalyzed by a Pt/phosphine complex to give the corresponding allylamines along with water as the sole by-product. Under optimized reaction conditions, primary allylamines were obtained as major products with excellent monoallylation selectivity. cod=1,5-cyclooctadiene.
Chemoselective reduction of azides catalyzed by molybdenum xanthate by using phenylsilane as the hydride source
Maddani, Mahagundappa R.,Moorthy, Saravana K.,Prabhu, Kandikere R.
supporting information; experimental part, p. 329 - 333 (2010/03/01)
A chemoselective, neutral, and efficient strategy for the reduction of azides to corresponding amines catalyzed by dioxobis(N,N,-diethyldithiocarbamato) molybdenum complex (1, MoO2[S2CNEt2]2) in the presence of phenylsilane is discovered. This chemoselective reduction strategy tolerates a variety of reducible functional groups.
Dramatic effect of boron-based Lewis acids in cross-metathesis reactions
Vedrenne, Emeline,Dupont, Hervé,Oualef, Sabrina,Elka?m, Laurent,Grimaud, Laurence
, p. 670 - 672 (2007/10/03)
Amino compounds such as allylic carbamates or amides are poor partners in cross-metathesis reactions because of possible coordination of the emerging carbene to the polar functional group. Whereas the use of titanium Lewis acid catalysts was unsatisfactor
Asymmetric syntheses of N-Boc 2-substituted pyrrolidines and piperidines by intramolecular cyclization
Serino,Stehle,Yong Sun Park,Florio,Beak
, p. 1160 - 1165 (2007/10/03)
Asymmetric lithiation-substitutions by n-BuLi/(-)-sparteine with the N- Boc-N-(3-halopropyl)allylamines 1-4 provide the N-Boc-2-alkenylpyrrolidines (S)-5, (S)-6, and (S)-7 in yields of 3193% with enantiomeric ratios (ers) from 65:35 to 90:10. These reactions are shown to involve an initial asymmetric deprotonation, but the enantiodetermining step is a subsequent asymmetric cyclization under the influence of the chiral ligand. Extension to formation of a piperidine is illustrated by reaction of N-Boc-(4- chlorobutyl)cinnamylamine (9) to afford (S)-N-Boc-2-(trans-β- styryl)piperidine ((S)-10) in 68% yield with an enantiomeric ratio (er) of 84:16. Analogous reactions with epoxide ring openings of N-Boc-N- (oxaalkenyl)benzylamines 11 and 12 afford the corresponding N-Boc-2-phenyl- 3-(hydroxymethyl)pyrrolidine (13) in 67% yield with a diastereomeric ratio (dr) of 50:50 and ers of 97:3 and 95:5 and the corresponding N-Boc-2-phenyl- 3-(hydroxymethyl)piperidine (14) in 29% yield with a dr of 86:14 and ers of 81:19 and 86:14.
Novel Tandem Conjugate Addition-Ramberg-B?cklund Rearrangements
Evans, Paul,Taylor, Richard J. K.
, p. 1043 - 1044 (2007/10/03)
A novel tandem process is reported for the preparation of allylic amines, ethers and sulfides from α-bromo-α,β-unsaturated sulfones; this process is believed to proceed via an initial conjugate addition followed by proton exchange and Ramberg-Ba?cklund rearrangement.
