222016-65-1Relevant academic research and scientific papers
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.
Enantioselective assembly of tertiary stereocenters via multicomponent chemoselective cross-coupling of geminal chloro(iodo)alkanes
Jiang,Kulbitski,Nisnevich,Gandelman
, p. 2762 - 2767 (2016/04/05)
Tertiary stereocenters represent a ubiquitous and highly important motif in many pharmaceutically active compounds and natural products. Development of efficient and straightforward approaches to their enantioselective construction from readily available simple substrates is an important yet challenging goal for synthetic chemistry. Herein we describe an efficient, versatile and facile method for the highly enantioselective construction of tertiary stereocenters via unprecedented consecutive one-pot Suzuki reactions of non-activated racemic 1-chloro-1-iodoalkanes with alkylboranes. It represents the first cross-coupling approach which employs simple and readily available primary alkyl substrates for the direct multicomponent assembly of enantioenriched tertiary stereocenters. A simple and effective preparation of 1-chloro-1-iodoalkanes from ubiquitous α-chloroalkanoic acids is also described. Collectively, the developed methods open a door to efficient catalytic enantioselective synthesis of alkanes bearing tertiary stereocenters from carboxylic acids just in few steps.
Highly enantiomerically enriched α-haloalkyl grignard reagents
Hoffmann, Reinhard W.,Nell, Peter G.,Leo, Roland,Harms, Klaus
, p. 3359 - 3365 (2007/10/03)
α-Chloro- and α-bromoalkyl Grignard reagents 11 and 30 with > 97% ee (enantiomeric excess) were generated by a sulfoxide/magnesium exchange reaction from the enantiomerically and diastereomerically pure sulfoxides 25 and 27. The resulting α-haloalkyl Grig
