74120-62-0Relevant academic research and scientific papers
Dual Benzophenone/Copper-Photocatalyzed Giese-Type Alkylation of C(sp3)?H Bonds
Abadie, Baptiste,Jardel, Damien,Pozzi, Gianluca,Toullec, Patrick,Vincent, Jean-Marc
supporting information, p. 16120 - 16127 (2019/11/26)
Photocatalyzed Giese-type alkylations of C(sp3)?H bonds are very attractive reactions in the context of atom-economy in C?C bond formation. The main limitation of such reactions is that when using highly polymerizable olefin acceptors, such as unsubstituted acrylates, acrylonitrile, or methyl vinyl ketone, radical polymerization often becomes the dominant or exclusive reaction pathway. Herein, we report that the polymerization of such olefins is strongly limited or suppressed when combining the photocatalytic activity of benzophenone (BP) with a catalytic amount of Cu(OAc)2. Under mild and operationally simple conditions, the Giese adducts resulting from the C(sp3)?H functionalization of amines, alcohols, ethers, and cycloalkanes could be synthesized. Preliminary mechanistic studies have revealed that the reaction does not proceed through a radical chain, but through a dual BP/Cu photocatalytic process, in which both CuII and low-valent CuI/0 species, generated in situ by reduction by the BP ketyl radical, may react with α-keto or α-cyano intermediate radicals, thus preventing polymerization.
Synthesis of Secondary Unsaturated Lactams via an Aza-Heck Reaction
Shuler, Scott A.,Yin, Guoyin,Krause, Sarah B.,Vesper, Caroline M.,Watson, Donald A.
supporting information, p. 13830 - 13833 (2016/11/06)
The preparation of unsaturated secondary lactams via the palladium-catalyzed cyclization of O-phenyl hydroxamates onto a pendent alkene is reported. This method provides rapid access to a broad range of lactams that are widely useful building blocks in alkaloid synthesis. Mechanistic studies support an aza-Heck-type pathway.
Homoaldol and aldol reactions from common enolates and oxirance: Reaction of reductively generated chromium enolates through cationic rearrangement
Hojo, Makoto,Sakata, Kyosuke,Maimaiti, Xiamuxikamaer,Ueno, Junya,Nishikori, Hisashi,Hosomi, Akira
, p. 142 - 143 (2007/10/03)
Enolates generated from α-bromo esters by the reduction with Bu6CrLi3 react with oxiranes to afford γ-hydroxy esters and β-hydroxy esters, depending on the Lewis acid used as a promoter.
Divalent Lanthanide Derivatives in Organic Synthesis. 1. Mild Preparation of SmI2 and YbI2 and Their Use as Reducing or Coupling Agents
Girard, P.,Namy, J. L.,Kagan, H. B.
, p. 2693 - 2698 (2007/10/02)
The facile synthesis of SmI2 and YbI2 from corresponding metals in THF is described.The reactivity of these potentially powerful reducing agents toward a variety functional groups is tested.Epoxides and sulfoxides are deoxygenated.Aldehydes are selectively reduced in presence of ketones.Alkyl halides or tosylates are converted into alkanes.Only coupling products are obtained from benzylic or allylic halides.In the presence of a SmI2-THF solution, tertiary alcohols are easily obtained from reactions between ketones and alkyl halides.In a similar manner, SmI2 promotes straightforward alkylation of ketones by alkyl sulfonates.Selective addition of polyfunctional halides or tosylates to ketones may be performed.In these reactions, catalytic amounts of FeCl3 enhance the reactivity.
