5005-72-1Relevant articles and documents
Titanium-Catalyzed Intermolecular Hydroaminoalkylation of Alkenes with Tertiary Amines
Geik, Dennis,Rosien, Michael,Bielefeld, Jens,Schmidtmann, Marc,Doye, Sven
supporting information, p. 9936 - 9940 (2021/03/31)
The first cationic titanium catalyst system for the intermolecular hydroaminoalkylation of alkenes with various tertiary alkylamines is presented. Corresponding reactions which involve the addition of the α-C?H bond of a tertiary amine across the C?C double bond of an alkene take place at temperatures close to room temperature with excellent regioselectivity to deliver the branched products exclusively. Interestingly, for selected amines, α-C?H bond activation occurs not only at N-methyl but also at N-methylene groups.
Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives
Rong, Xiaona,Guo, Jingwen,Hu, Zheqi,Huang, Lehao,Gu, Yugui,Cai, Yuepiao,Liang, Guang,Xia, Qinqin
supporting information, p. 701 - 708 (2020/12/30)
An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines
Musacchio, Andrew J.,Lainhart, Brendan C.,Zhang, Xin,Naguib, Saeed G.,Sherwood, Trevor C.,Knowles, Robert R.
, p. 727 - 730 (2017/02/26)
The intermolecular hydroamination of unactivated alkenes with simple dialkyl amines remains an unsolved problem in organic synthesis. We report a catalytic protocol for efficient additions of cyclic and acyclic secondary alkyl amines to a wide range of alkyl olefins with complete anti-Markovnikov regioselectivity. In this process, carbon-nitrogen bond formation proceeds through a key aminium radical cation intermediate that is generated via electron transfer between an excited-state iridium photocatalyst and an amine substrate. These reactions are redox-neutral and completely atom-economical, exhibit broad functional group tolerance, and occur readily at room temperature under visible light irradiation. Certain tertiary amine products generated through this method are formally endergonic relative to their constituent olefin and amine starting materials and thus are not accessible via direct coupling with conventional ground-state catalysts.