60834-63-1Relevant articles and documents
Scalable Negishi Coupling between Organozinc Compounds and (Hetero)Aryl Bromides under Aerobic Conditions when using Bulk Water or Deep Eutectic Solvents with no Additional Ligands
Dilauro, Giuseppe,Azzollini, Claudia S.,Vitale, Paola,Salomone, Antonio,Perna, Filippo M.,Capriati, Vito
supporting information, p. 10632 - 10636 (2021/04/09)
Pd-catalyzed Negishi cross-coupling reactions between organozinc compounds and (hetero)aryl bromides have been reported when using bulk water as the reaction medium in the presence of NaCl or the biodegradable choline chloride/urea eutectic mixture. Both C(sp3)-C(sp2) and C(sp2)-C(sp2) couplings have been found to proceed smoothly, with high chemoselectivity, under mild conditions (room temperature or 60 °C) in air, and in competition with protonolysis. Additional benefits include very short reaction times (20 s), good to excellent yields (up to 98 %), wide substrate scope, and the tolerance of a variety of functional groups. The proposed novel protocol is scalable, and the practicability of the method is further highlighted by an easy recycling of both the catalyst and the eutectic mixture or water.
Aza versus Oxophilicity of SmI2: A Break of a Paradigm
Maity, Sandeepan,Flowers, Robert A.,Hoz, Shmaryahu
supporting information, p. 17070 - 17077 (2017/11/13)
Ligands that coordinate to SmI2 through oxygen are prevalent in the literature and make up a significant portion of additives employed with the reagent to perform reactions of great synthetic importance. In the present work a series of spectroscopic, calorimetric and kinetic studies demonstrate that nitrogen-based analogues of many common additives have a significantly higher affinity for Sm than the oxygen-based counterparts. In addition, electrochemical experiments show that nitrogen-based ligands significantly enhance the reducing power of SmI2. Overall, this work demonstrates that the use of nitrogen-based ligands provides a useful alternative approach to enhance the reactivity of reductants based on SmII.
Direct catalytic cross-coupling of organolithium compounds
Giannerini, Massimo,Fananas-Mastral, Martin,Feringa, Ben L.
, p. 667 - 672 (2013/08/23)
Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.
