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71.
Pd‐PEPPSI‐IHeptCl: A General‐Purpose,Highly Reactive Catalyst for the Selective Coupling of Secondary Alkyl Organozincs
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Dr. Bruce Atwater Dr. Nalin Chandrasoma Dr. David Mitchell Dr. Michael J. Rodriguez Prof. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14531-14534
Dichloro[1,3‐bis(2,6‐di‐4‐heptylphenyl)imidazol‐2‐ylidene](3‐chloropyridyl)palladium(II) (Pd‐PEPPSI‐IHeptCl), a new, very bulky yet flexible Pd–N‐heterocyclic carbene (NHC) complex has been evaluated in the cross‐coupling of secondary alkylzinc reactants with a wide variety of oxidative addition partners in high yields and excellent selectivity. The desired, direct reductive elimination branched products were obtained with no sign of migratory insertion across electron‐rich and electron‐poor aromatics and all forms of heteroaromatics (five and six membered). Impressively, there is no impact of substituents at the site of reductive elimination (i.e., ortho or even di‐ortho), which has not yet been demonstrated by another catalyst system to date. 相似文献
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Tharwat Mohy El Dine David Evans Prof. Jacques Rouden Dr. Jérôme Blanchet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5894-5898
A highly efficient and mild transamidation of amides with amines co‐catalysed by borinic acid and acetic acid has been reported. A wide range of functionalised formamides was synthesized in excellent yields, including important chiral α‐amino acid derivatives, with minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron‐derived Lewis acidity rather than an improved Brønsted acidity of acetic acid. 相似文献
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Adrian Tlahuext‐Aca Dr. Matthew N. Hopkinson R. Aleyda Garza‐Sanchez Prof. Dr. Frank Glorius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5909-5913
Highly selective tandem nucleophilic addition/cross‐coupling reactions of alkynes have been developed using visible‐light‐promoted dual gold/photoredox catalysis. The simultaneous oxidation of AuI and coordination of the coupling partner by photo‐generated aryl radicals, and the use of catalytically inactive gold precatalysts allows for high levels of selectivity for the cross‐coupled products without competing hydrofunctionalization or homocoupling. As demonstrated in representative arylative Meyer–Schuster and hydration reactions, this work expands the scope of dual gold/photoredox catalysis to the largest class of substrates for gold catalysts and benefits from the mild and environmentally attractive nature of visible‐light activation. 相似文献
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Dr. Martin Pichette Drapeau Prof. Dr. Lukas J. Gooßen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18654-18677
The selective transformation of C?H bonds is one of the most desirable approaches to creating complexity from simple building blocks. Several directing groups are efficient in controlling the regioselectivity of catalytic C?H bond functionalizations. Among them, carboxylic acids are particularly advantageous, since they are widely available in great structural diversity and at low cost. The carboxylate directing groups can be tracelessly cleaved or may serve as the anchor point for further functionalization through decarboxylative couplings. This Minireview summarizes the substantial progress made in the last few years in the development of reactions in which carboxylate groups direct C?H bond functionalizations with formation of C?C, C?O, C?N, or C?halogen bonds at specific positions. It is divided into sections on C?C, C?O, C?N, and C?halogen bond formation, each of which is subdivided by reactions and product classes. Particular emphasis is placed on methods that enable multiple derivatizations by combining carboxylate‐directed C?H functionalization with decarboxylative couplings. 相似文献
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