59339-34-3Relevant academic research and scientific papers
Preparation of Optically Enriched Secondary Alkyllithium and Alkylcopper Reagents—Synthesis of (?)-Lardolure and Siphonarienal
Morozova, Varvara,Skotnitzki, Juri,Moriya, Kohei,Karaghiosoff, Konstantin,Knochel, Paul
, p. 5516 - 5519 (2018)
Optically enriched secondary alkyl iodides were converted into secondary alkyllithium and secondary alkylcopper compounds with very high retention of configuration. Quenching with various electrophiles, including chiral epoxides, provided a range of chira
A Concise and Atom-Economical Suzuki-Miyaura Coupling Reaction Using Unactivated Trialkyl- and Triarylboranes with Aryl Halides
Li, Hongmei,Zhong, Yong-Li,Chen, Cheng-Yi,Ferraro, Ashley E.,Wang, Dengjin
supporting information, p. 3616 - 3619 (2015/07/28)
A concise and atom-economical Suzuki-Miyaura coupling of trialkyl- and triarylboranes with aryl halides is described. This new protocol represents the first general, practical method that efficiently utilizes peralkyl and peraryl groups of the unactivated trialkyl- and triarylboranes for the Suzuki-Miyaura coupling reaction.
C-H bond functionalization via hydride transfer: Formation of α-arylated piperidines and 1,2,3,4-tetrahydroisoquinolines via stereoselective intramolecular amination of benzylic C-H bonds
Vadola, Paul A.,Carrera, Ignacio,Sames, Dalibor
, p. 6689 - 6702 (2012/10/18)
We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl aldehydes are subjected to N-toluenesulfonamide in the presence of BF3?OEt2 to effect imine formation and HT-cyclization, leading to 2-arylpiperidines and 3-aryl-1,2,3,4- tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexibility. Substrates of higher conformational rigidity were more reactive, giving higher yields of the desired products. However, a single substituent on the alkyl chain linking the N-tosylimine and the benzylic sp3 C-H bonds was sufficient for HT-cyclization to occur. In addition, an examination of various arenes revealed that the electronic character of the hydridic C-H bonds dramatically affects the efficiency of the reaction. We also found that this transformation is highly stereoselective; 2-substituted aldehydes yield cis-2,5-disubstituted piperidines, while 3-substituted aldehydes afford trans-2,4-disubstituted piperidines. The stereoselectivity is a consequence of thermodynamic control. The pseudoallylic strain between the arene and tosyl group on the piperidine ring is proposed to rationalize the greater stability of the isomer with the aryl ring in the axial position. This preferential placement of the arene is proposed to affect the observed stereoselectivity.
