64343-08-4Relevant articles and documents
Chemoselective Homologation-Deoxygenation Strategy Enabling the Direct Conversion of Carbonyls into (n+1)-Halomethyl-Alkanes
Citarella, Andrea,Holzer, Wolfgang,Ielo, Laura,Langer, Thierry,Miele, Margherita,Pace, Vittorio,Urban, Ernst,Zehl, Martin
supporting information, p. 7629 - 7634 (2020/10/12)
The sequential installation of a carbenoid and a hydride into a carbonyl, furnishing halomethyl alkyl derivatives, is reported. Despite the employment of carbenoids as nucleophiles in reactions with carbon-centered electrophiles, sp3-type alkyl halides remain elusive materials for selective one-carbon homologations. Our tactic levers on using carbonyls as starting materials and enables uniformly high yields and chemocontrol. The tactic is flexible and is not limited to carbenoids. Also, diverse carbanion-like species can act as nucleophiles, thus making it of general applicability.
Free Radical Substitution. Part 38. The Effect of Solvent on the Atomic Chlorination and Bromination of 2-Substituted Butanes and the Importance of Steric Effects
Atto, Saeed Y.,Tedder, John M.,Walton, John C.
, p. 629 - 634 (2007/10/02)
The relative selectivity of atomic halogenation of 2-substituted butanes is influenced by the phase and by solvents.There are solvents which increase the selectivity compared with the gas phase and solvents which decrease the relative selectivity.However the most striking feature of the halogenation (especially the bromination) of 2-substituted butanes is the high reactivity of the 2-position notwithstanding very unfavourable polar effects.This reactivity is attributed to the release of steric compression associated with the abstraction of the tertiary hydrogen atom.The halogenation of butan-2-ol esters is associated with some decomposition of 2-butyl radical (OCOR)CH3> and the chlorination of 2-phenylbutane with the formation of olefins 2-phenylbut -1-ene and 2-phenylbut-2-ene.