136608-30-5Relevant academic research and scientific papers
Room-temperature Hiyama cross-couplings of arylsilanes with alkyl bromides and iodides
Lee, Jae-Young,Fu, Gregory C.
, p. 5616 - 5617 (2003)
The first method for achieving Hiyama couplings of unactivated alkyl bromides and iodides is reported. The desired carbon-carbon bond formation proceeds under mild conditions (room temperature) with good functional-group tolerance. Copyright
Copper-catalyzed sp3-sp3 cross-coupling of turbo grignards with benzyl halides
Elahi-Mohassel, Synah,Girgis, Michael,Paige, Mikell,Petruncio, Greg
supporting information, (2021/11/17)
The aromatic ring in benzyl halides and sulfonates imparts unique reactivity at the benzylic carbon atom. Photoredox sp3-sp3 cross-coupling proved ineffective for coupling p-methoxybenzyl chloride (PMBCl), leading to a new strategy for the sp3-sp3 cross-coupling of benzyl halides and sulfonates. This strategy involved LiCl-accelerated synthesis of a Grignard reagent followed by a copper-catalyzed cross-coupling. The conditions worked well for PMBCl due to its exceptional reactivity but other benzyl bromides or sulfonates reacted poorly.
Electroreductive Carbofunctionalization of Alkenes with Alkyl Bromides via a Radical-Polar Crossover Mechanism
Zhang, Wen,Lin, Song
supporting information, p. 20661 - 20670 (2020/12/23)
Electrochemistry grants direct access to reactive intermediates (radicals and ions) in a controlled fashion toward selective organic transformations. This feature has been demonstrated in a variety of alkene functionalization reactions, most of which proceed via an anodic oxidation pathway. In this report, we further expand the scope of electrochemistry to the reductive functionalization of alkenes. In particular, the strategic choice of reagents and reaction conditions enabled a radical-polar crossover pathway wherein two distinct electrophiles can be added across an alkene in a highly chemo- and regioselective fashion. Specifically, we used this strategy in the intermolecular carboformylation, anti-Markovnikov hydroalkylation, and carbocarboxylation of alkenes - reactions with rare precedents in the literature - by means of the electroreductive generation of alkyl radical and carbanion intermediates. These reactions employ readily available starting materials (alkyl halides, alkenes, etc.) and simple, transition-metal-free conditions and display broad substrate scope and good tolerance of functional groups. A uniform protocol can be used to achieve all three transformations by simply altering the reaction medium. This development provides a new avenue for constructing Csp3-Csp3 bonds.
Synthesis of quinolinyl-based pincer copper(ii) complexes: an efficient catalyst system for Kumada coupling of alkyl chlorides and bromides with alkyl Grignard reagents
Pandiri, Hanumanprasad,Gonnade, Rajesh G.,Punji, Benudhar
supporting information, p. 16747 - 16754 (2018/12/05)
Quinolinamide-based pincer copper(ii) complexes, κN,κN,κN-{C9H6N-(μ-N)-C(O)CH2NEt2}CuX [(QNNNEt2)CuX (X = Cl, 2; X = Br, 3; X = OAc, 4)], were synthesized by the reaction of ligand (QNNNEt2)-H (1) with CuX2 (X = Cl, Br or OAc) in the presence of Et3N. The reaction of (QNNNEt2)-H with CuX (X = Cl, Br or OAc) also afforded the Cu(ii) complexes 2, 3 and 4, respectively, instead of the expected Cu(i) pincer complexes. The formation of Cu(ii) complexes from Cu(i) precursors most likely occurred via the disproportionation reaction of Cu(i) into Cu(0) and Cu(ii). A cationic complex [(QNNNEt2)Cu(CH3CN)]OTf (5) was synthesized by the treatment of neutral complex 2 with AgOTf. On the other hand, the reaction of (QNNNEt2)-H (1) with [Cu(MeCN)4]ClO4 produced cationic Cu(i) complex, [(QNN(H)NEt2)Cu(CH3CN)]ClO4 (6), in good yield. All complexes 2-5 were characterized by elemental analysis and HRMS measurements. Furthermore, the molecular structures of 2, 3 and 4 were elucidated by X-ray crystallography. Complex 4 crystallizes in a dimeric and catemeric pattern. The cationic complex 5 was found to be an efficient catalyst for the Kumada coupling reaction of diverse nonactivated alkyl chlorides and bromides with alkyl magnesium chloride under mild reaction conditions.
