935-56-8Relevant articles and documents
Schwartz,Moon
, p. 865,868 (1975)
Alkylphosphinites as Synthons for Stabilized Carbocations
Ochmann, Lukas,Kessler, Mika L.,Schreiner, Peter R.
supporting information, p. 1460 - 1464 (2022/03/01)
We present a new acid-free method for the generation of carbocations based on a redox condensation reaction that enables SN1 reactions with a variety of nucleophiles. We utilize readily synthesized phosphinites that are activated by diisopropyl azodicarboxylate to form betaine structures that collapse upon adding a pronucleophile, thereby yielding reactive carbocation intermediates. We also employ this approach for the alkylation of some bioactive molecules.
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 C-C Single-Bond Cleavage of Alcohols
Liu, Wei,Wu, Qiang,Wang, Miao,Huang, Yahao,Hu, Peng
supporting information, p. 8413 - 8418 (2021/11/01)
An iron-catalyzed deconstruction/hydrogenation reaction of alcohols through C-C bond cleavage is developed through photocatalysis, to produce ketones or aldehydes as the products. Tertiary, secondary, and primary alcohols bearing a wide range of substituents are suitable substrates. Complex natural alcohols can also perform the transformation selectively. A investigation of the mechanism reveals a procedure that involves chlorine radical improved O-H homolysis, with the assistance of 2,4,6-collidine.