18094-01-4Relevant articles and documents
Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst
Bennett, Elliot L.,Brookfield, Adam,Guan, Renpeng,Huang, Zhiliang,Mcinnes, Eric J. L.,Robertson, Craig M.,Shanmugam, Muralidharan,Xiao, Jianliang
, p. 10005 - 10013 (2021/07/19)
The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.
Triflimide-catalysed sigmatropic rearrangement of N-allylhydrazones as an example of a traceless bond construction
Mundal, Devon A.,Avetta Jr., Christopher T.,Thomson, Regan J.
supporting information; experimental part, p. 294 - 297 (2010/09/12)
The recognition of structural elements (that is, retrons) that signal the application of specific chemical transformations is a key cognitive event in the design of synthetic routes to complex molecules. Reactions that produce compounds without an easily identifiable retron, by way of either substantial structural rearrangement or loss of the atoms required for the reaction to proceed, are significantly more difficult to apply during retrosynthetic planning, yet allow for non-traditional pathways that may facilitate efficient acquisition of the target molecule. We have developed a triflimide (Tf 2 NH)-catalysed rearrangement of N-allylhydrazones that allows for the generation of a sigma bond between two unfunctionalized sp 3 carbons in such a way that no clear retron for the reaction remains. This new traceless bond construction displays a broad substrate profile and should open avenues for synthesizing complex molecules using non-traditional disconnections.
A Facile Method for Synthesis of Alkyl Phenyl Selenides. The Reaction of Diphenyl Diselenide with Oxygen-containing Compounds Using La/Me 3SiCl/cat.I2/cat.CuI System
Nishino, Toshiki,Nishiyama, Yutaka,Sonoda, Noboru
, p. 918 - 919 (2007/10/03)
Alcohols, ethers, and esters were directly converted to the corresponding alkyl phenyl selenides by the reaction of diphenyl diselenide and the La/Me 3SiCl/cat.I2/cat.CuI. It was suggested that alkyl phenyl sele
