10496-20-5Relevant academic research and scientific papers
Chemoselective Union of Olefins, Organohalides, and Redox-Active Esters Enables Regioselective Alkene Dialkylation
Yang, Tao,Jiang, Yi,Luo, Yixin,Lim, Joel Jun Han,Lan, Yu,Koh, Ming Joo
supporting information, p. 21410 - 21419 (2021/01/11)
Multicomponent catalytic processes that can generate multiple C(sp3)-C(sp3) bonds in a single step under mild conditions, particularly those that employ inexpensive catalysts and substrates, are highly sought-after in chemistry research for complex molecule synthesis. Here, we disclose an efficient Ni-catalyzed reductive protocol that chemoselectively merges alkenyl amides with two different aliphatic electrophiles. Starting materials are readily accessible from stable and abundant feedstock, and products are furnished in up to >98:2 regioisomeric ratios. The present strategy eliminates the use of sensitive organometallic reagents, tolerates a wide array of complex functionalities, and enables regiodivergent addition of two primary alkyl groups bearing similar electronic and steric attributes across aliphatic C=C bonds with exquisite control of site selectivity. Utility is underscored by the concise synthesis of bioactive compounds and postreaction functionalizations leading to structurally diverse scaffolds. DFT studies revealed that the regiochemical outcome originates from the orthogonal reactivity and chemoselectivity profiles of in situ generated organonickel species.
Iron-Catalyzed Vinylic C?H Alkylation with Alkyl Peroxides
Ge, Liang,Jian, Wujun,Zhou, Huan,Chen, Shaowei,Ye, Changqing,Yu, Fei,Qian, Bo,Li, Yajun,Bao, Hongli
supporting information, p. 2522 - 2528 (2018/08/01)
A variety of alkyl peresters and alkyl diacyl peroxides, which are readily accessible from carboxylic acids, are utilized as general primary, secondary, and tertiary alkylating reagents for iron-catalyzed vinylic C?H alkylation of vinyl arenes, dienes, and 1,3-enynes. This transformation affords olefinic products in up to 98 % yield with high E/Z values. A broad range of functionalities, including carboxyl, boronic acid, methoxy, ester, amino, and halides, are tolerated. This protocol provides a facile approach to some olefins that are difficult to access, and hence, offers an alternative to existing systems. The synthetic utility of this method is demonstrated by late-stage functionalization of selected natural-product derivatives.
Fluorine transfer to alkyl radicals
Rueda-Becerril, Montserrat,Chatalova Sazepin, Claire,Leung, Joe C. T.,Okbinoglu, Tulin,Kennepohl, Pierre,Paquin, Jean-Francois,Sammis, Glenn M.
supporting information; experimental part, p. 4026 - 4029 (2012/04/10)
The development of new synthetic technologies for the selective fluorination of organic compounds has increased with the escalating importance of fluorine-containing pharmaceuticals. Traditional methods potentially applicable to drug synthesis rely on the use of ionic forms of fluorine (F - or F+). Radical methods, while potentially attractive as a complementary approach, are hindered by a paucity of safe sources of atomic fluorine (F?). A new approach to alkyl fluorination has been developed that utilizes the reagent N-fluorobenzenesulfonimide as a fluorine transfer agent to alkyl radicals. This approach is successful for a broad range of alkyl radicals, including primary, secondary, tertiary, benzylic, and heteroatom-stabilized radicals. Furthermore, calculations reveal that fluorine-containing ionic reagents are likely candidates for further expansion of this approach to polar reaction media. The use of these reagents in alkyl radical fluorination has the potential to enable powerful new transformations that otherwise would take multiple synthetic steps.
