78742-75-3Relevant academic research and scientific papers
Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids
Mao, Runze,Bera, Srikrishna,Turla, Aurélya Christelle,Hu, Xile
supporting information, p. 14667 - 14675 (2021/09/18)
Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.
Iron-Catalyzed Thiolation and Selenylation of Cycloalkyl Hydroperoxides via C-C Bond Cleavage
Sun, Qing-Xin,Chen, He,Liu, Shuai,Wang, Xiao-Qiang,Duan, Xin-Hua,Guo, Li-Na
, p. 11987 - 11997 (2021/09/02)
A cheap iron-catalyzed C-C bond cleavage/thiolation and selenylation of cycloalkyl hydroperoxides are presented. This redox-neutral protocol provides efficient access to diverse distal keto-functionalized thioethers and selenium compounds. Remarkably, only some amounts of disulfides are required for this transformation.
Dealkenylative Thiylation of C(sp3)-C(sp2) Bonds
Smaligo, Andrew J.,Kwon, Ohyun
supporting information, p. 8592 - 8597 (2019/10/14)
Carbon-carbon bond fragmentations are useful methods for the functionalization of molecules. The value of such cleavage events is maximized when paired with subsequent bond formation. Herein we report a protocol for the cleavage of an alkene C(sp3)-C(sp2) bond, followed by the formation of a new C(sp3)-S bond. This reaction is performed in nonanhydrous solvent and open to the air, employs common starting materials, and can be used to rapidly diversify natural products.
Preparation and Reactions of Novel Cyclic β-Oxosulphonium Salts obtained by the Acid-induced Cycisation of 1-Diazo-ω-phenylthio-2-alkanones
Flowers, William T.,Freitas, Ana M.,Holt, Geoffrey,Purkiss, Stuart C.
, p. 1119 - 1124 (2007/10/02)
With perchloric acid, the diazo-ketones PhSnCOCHN2 (1a)-(1d) give the corresponding cyclic β-oxosulphonium salts (2a)-(2d); the p-chlorophenyl analogue of (2d) was similarly prepared.The salts (2a), (2c), and (2d) react with triphenylphosphine at C(2) to give the acyclic phosphonium salts (3a), (3c), and (3d) and, analogously, with potassium O-ethyl dithiocarbonate to give the corresponding acyclic O-ethyl dithiocarbonates (3f), (3g), and (3h).All the reactions of the salt (2b) with nucleophiles gave either 1-phenylthiobut-3-en-2-one (11) or products of its Michael addition.Salts (2c) and (2d) with sodium methoxide in methanol provide, respectively, methyl ω-phenylthio-butanoate and -pentanoate in a process that involves the loss of a methylene group.These and other reactions are considered to proceed via ylide intermediates; the intermediate derived by the deprotonation of (2d) being isolated, whereas that from (2c) rearranged to give 3-phenylthiocyclopentanone.
