172325-42-7Relevant articles and documents
Reversibility of Ketone Reduction by SmI2-Water and Formation of Organosamarium Intermediates
Chciuk, Tesia V.,Anderson, William R.,Flowers, Robert A.
, p. 4579 - 4583 (2017/12/18)
The reduction of ketones by SmI2-water has long been thought to proceed through a reversible initial electron transfer with the formation of organosamarium intermediates in a follow-up step. Kinetic experiments on the reduction of two model ketones and structurally similar ketones with a pendant alkene are shown to be consistent with a rate-limiting reduction by SmI2-water through a proton-coupled electron-transfer (PCET). Literature values for the rates of radical cyclizations and reduction of radicals by SmI2 and thermochemical data for radical reduction by SmI2-water further support a rate-limiting initial step for ketone reductions. These data suggest that discrete organosamarium species may not be intermediates in ketone reductions by SmI2-water.
Rhodium(iii)-catalyzed allylic C-H bond amination. Synthesis of cyclic amines from ω-unsaturated N-sulfonylamines
Cochet, Thomas,Bellosta, Veronique,Roche, Didier,Ortholand, Jean-Yves,Greiner, Alfred,Cossy, Janine
supporting information, p. 10745 - 10747 (2013/01/15)
For the first time, intramolecular allylic amination was conducted using rhodium(iii) according to an "inner-sphere" type mechanism with amines activated by only one electron-withdrawing group. The activation of C(sp 3)-H bonds was chemoselective and allows the access to a variety of substituted cyclic amines such as pyrrolidines and piperidines.
Hydroxyl-directed cyclopropanation of Z-allylsilanes
Mohr, Peter
, p. 7221 - 7224 (2007/10/02)
Z-5-Hydroxy-alk-2-enyl-silanes of general structure 1 are cyclopropanated by an excess of CH2l2 / Et2Zn in good yield and excellent stereoselectivity. Ensuing protodesilylation, however, lacks efficient regiocontrol and affords syn-products 5 in modest yield but high stereochemical purity.
