14759-74-1Relevant articles and documents
Catalyzed Rearrangements of Ten-Membered-Ring Allenes
Thies, Richard W.,Boop, Janice L.,Schiedler, Michael,Zimmerman, David C.,LaPage, Theodore H.
, p. 2021 - 2024 (1983)
Cyclodeca-1,2,5,8-tetraene (1) is shown to rearrange in the presence of various catalysts in acetic acid to cis,syn-tricyclo2,4>deca-5,8-diene (5) which is accompanied in some cases by rearranged acetate products, principally cis,syn-bicyclodeca-4,8-dien-2-yl acetate (3).Cyclodeca-1,2,5-triene (6) rearranges in a similar way, except that acetate product was only observed for Ag(I) catalysts.A related allene, bicyclodeca-2,3-diene underwent normal oxymercuration without rearrangement.
Chemoselective Oxidation of Equatorial Alcohols with N-Ligated λ3-Iodanes
Mikhael, Myriam,Adler, Sophia A.,Wengryniuk, Sarah E.
supporting information, p. 5889 - 5893 (2019/08/26)
The site-selective and chemoselective functionalization of alcohols in complex polyols remains a formidable synthetic challenge. Whereas significant advancements have been made in selective derivatization at the oxygen center, chemoselective oxidation to the corresponding carbonyls is less developed. In cyclic systems, whereas the selective oxidation of axial alcohols is well known, a complementary equatorial selective process has not yet been reported. Herein we report the utility of nitrogen-ligated (bis)cationic λ3-iodanes (N-HVIs) for alcohol oxidation and their unprecedented levels of selectivity for the oxidation of equatorial over axial alcohols. The conditions are mild, and the simple pyridine-ligated reagent (Py-HVI) is readily synthesized from commercial PhI(OAc)2 and can be either isolated or generated in situ. Conformational selectivity is demonstrated in both flexible 1,2-substituted cyclohexanols and rigid polyol scaffolds, providing chemists with a novel tool for chemoselective oxidation.
The Stereoselective Reductions of Ketones to the Most Thermodynamically Stable Alcohols Using Lithium and Hydrated Salts of Common Transition Metals
Kennedy, Nicole,Cohen, Theodore
, p. 8134 - 8141 (2015/09/02)
A simple method is presented for the highly stereoselective reductions of ketones to the most thermodynamically stable alcohols. In this procedure, the ketone is treated with lithium dispersion and either FeCl2·4H2O or CuCl2·2H2O in THF at room temperature. This protocol is applied to a large number and variety of ketones and is both more convenient and efficient than those commonly reported for the diastereoselective reduction of five- and six-membered cyclic ketones.
