66922-10-9Relevant academic research and scientific papers
Chiral Alkyl Amine Synthesis via Catalytic Enantioselective Hydroalkylation of Enecarbamates
Qian, Deyun,Bera, Srikrishna,Hu, Xile
supporting information, p. 1959 - 1967 (2021/02/06)
Chiral alkyl amines are omnipresent as bioactive molecules and synthetic intermediates. The catalytic and enantioselective synthesis of alkyl amines from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble a wide range of chiral alkyl amines from enecarbamates (N-Cbz-protected enamines) and alkyl halides with high regio- and enantioselectivity. The method works for both nonactivated and activated alkyl halides and is able to produce enantiomerically enriched amines with two minimally differentiated α-alkyl substituents. The mild conditions lead to high functional group tolerance, which is demonstrated in the postproduct functionalization of many natural products and drug molecules, as well as the synthesis of chiral building blocks and key intermediates to bioactive compounds.
Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light
Fu, Ming-Chen,Shang, Rui,Wang, Jia-Xin
supporting information, (2020/11/13)
Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid derived N-(acyloxy)phthalimide with lithium iodide as an iodine source. The reaction delivers primary, secondary, and bridgehead te
Control of Vicinal Stereocenters through Nickel-Catalyzed Alkyl–Alkyl Cross-Coupling
Mu, Xin,Shibata, Yu,Makida, Yusuke,Fu, Gregory C.
supporting information, p. 5821 - 5824 (2017/05/12)
Vicinal stereocenters are found in many natural and unnatural compounds. Although metal-catalyzed cross-coupling reactions of unactivated alkyl electrophiles are emerging as a powerful tool in organic synthesis, there have been virtually no reports of processes that generate, much less control, vicinal stereocenters. In this investigation, we establish that a chiral nickel catalyst can mediate doubly stereoconvergent alkyl–alkyl cross-coupling, specifically, reactions of a racemic pyrrolidine-derived nucleophile with cyclic alkyl halides (as mixtures of stereoisomers) to produce vicinal stereocenters with very good stereoselectivity.
Pd-catalyzed monoselective ortho -C-H alkylation of N -quinolyl benzamides: Evidence for stereoretentive coupling of secondary alkyl iodides
Zhang, Shu-Yu,Li, Qiong,He, Gang,Nack, William A.,Chen, Gong
supporting information, p. 531 - 539 (2015/01/30)
We report a method for the monoselective alkylation of ortho-C-H bonds of N-quinolyl benzamides with both primary and secondary alkyl halides under palladium catalysis. With promotion by NaHCO3 and (BnO)2PO2H or (PhO)
Mild and phosphine-free iron-catalyzed cross-coupling of nonactivated secondary alkyl halides with alkynyl grignard reagents
Cheung, Chi Wai,Ren, Peng,Hu, Xile
supporting information, p. 2566 - 2569 (2014/05/20)
A simple protocol for iron-catalyzed cross-coupling of nonactivated secondary alkyl bromides and iodides with alkynyl Grignard reagents at room temperature has been developed. A wide range of secondary alkyl halides and terminal alkynes are tolerated to a
Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions
Liu, Bo,Shine, Henry J.,Zhao, Wenyi
, p. 827 - 836 (2007/10/03)
Reactions of 5-(alkoxy)thianthrenium perchlorates (1) with weakly basic nucleophiles Br-, I- and PhS- (X-) in MeCN and DMSO led to SN2 substitution, E2C elimination, and reaction at sulfornium sulfur to extents depending on the structure of the alkoxy group (RO) in 1 and the nucleophile. Three types of reaction occurred with R = cyclopentyl (1a), cyclohexyl (1b), cis- (1c) and trans- 4-methylcyclohexyl (1d) and cycloheptyl (1e), and X- = Br and I-. That is, SN2 reaction gave RX and thianithrene 5-oxide (ThO), E2C reaction gave cycloalkene and ThO and reaction at sulfonium sulfur gave X2, thianthrene (Th) and cycloalkanol (ROH). Earlier work with R = Me (1f) and Et (1g) and X- = I-. Br- had shown that only SN2 reaction occurred. In contrast with reactions of halide ions, reactions of PhS- with 1b-g occurred only at sulfonium sulfur, giving Th, ROH and PhSSPh (DPDS). For comparison with 1, reactions of Ph2S+OMe (2) with I- and PhS- were carried out. Reaction with I- gave only Ph2S=O and Mel (SN2), Reaction with PhS- gave very little PhSMe (SN2) but mainly Ph2S, MeOH, and DPDS from reaction at sulfonium sulfur. The differences in nucleophilic pathways (PhS- vs Br- and I-) in reactions with 1 and 2 are attributed to differences in thiophilicities of the nucleophiles. The thiophilicity of PhS- dominates its reactions with 1 and 2. The direction toward products (Th, ROH and DPDS) in these reactions is compounded by the ease of displacement of alkoxide from 1 and 2 by PhS-, and the ease with which, subsequently, thiophilic PhS- attacks sulfenyl sulfur in the resulting phenylthiosulfonium ion. Copyright
