5558-87-2Relevant academic research and scientific papers
FACILE PALLADIUM CATALYZED DECARBOXYLATIVE ALLYLATION OF ACTIVE METHYLENE COMPOUNDS UNDER NEUTRAL CONDITIONS USING ALLYLIC CARBONATES
Tsuji, Jiro,Shimizu, Isao,Minami, Ichiro,Ohashi, Yukihiro
, p. 4809 - 4812 (1982)
Palladium catalyzed decarboxylative allylation of active methylene compounds proceeded under mild neutral conditions using allylic carbonates, which are much more reactive than allylic acetates or phenoxides used commonly in the reaction.
An extremely mild 3-aza-Claisen reaction. 2. New conditions and the rearrangement of α-heteroatom substituted amides
Walters,Hoem,Arcand,Hegeman,McDonough
, p. 1453 - 1456 (1993)
Several new and potentially useful reaction conditions for the 3-aza-Claisen rearrangement of N-allyl amides have been developed. These new conditions have been successfully applied to the rearrangement of α-heteroatom substituted species forming α-amino
Efficient and Clean Nickel Catalyzed α-Allylation Reaction of Nitriles
Mouhsine, Bouchaib,Karim, Abdallah,Dumont, Clément,Suisse, Isabelle,Sauthier, Mathieu
supporting information, p. 1457 - 1462 (2021/02/16)
A clean method has been developed for the α-allylation of phenyl and alpha alkyl phenyl acetonitrile with allylic alcohols. The reaction is catalyzed by nickel complexes in situ generated from a combination of Ni(cod)2 and the dppf ligand and performed at 80 °C in methanol as reaction solvent.Accordingly to this simple and base-free protocol that only yields water as a side-product, many allylic nitriles were synthetized with good yields. (Figure presented.).
Palladium(II)-Catalyzed Aminotrifluoromethoxylation of Alkenes: Mechanistic Insight into the Effect of N-Protecting Groups
Chen, Chaohuang,Chen, Pinhong,Hou, Chuanqi,Liu, Guosheng
supporting information, p. 346 - 350 (2020/05/25)
An efficient palladium-catalyzed regioselective 5-exo aminotrifluoromethoxylation of alkenes has been established herein, which provides a practical route towards the synthesis of OCF3-containing pyrrolidines. tert-Butyloxycarbonyl (Boc) as an amino protecting group plays a significant role in both the chemo- and regioselectivities. In addition, preliminary mechanistic studies reveal that the amino protecting group of substrates and the counter anion of palladium catalyst play critical roles in reaction efficiency presumably due to an isomerization of alkyl- Pd(II) intermediates. Moreover, the asymmetric 5-exo aminotrifluoromethoxylation reaction has also been achieved by introducing a sterically bulky pyridinyl-oxazoline ligand.
Surprising and Highly Efficient Use of Methylmagnesium Chloride as a Non-Nucleophilic Base in the Deprotonation and Alkylation of sp3 Centres Adjacent to Nitriles
Gbadebo, Omolola,Smith, Dennis,Harnett, Ger,Donegan, Gregory,O'Leary, Patrick
, p. 7037 - 7045 (2019/01/04)
Methylmagnesium chloride (MeMgCl) is a key reagent in research and industry typically as a nucleophile. In this article we develop the use of MeMgCl as a non-nucleophilic base in conjunction with catalytic amounts of an amine mediator. Specifically, we use the base to deprotonate α to a variety of nitriles in alkylation reactions, applying it to the synthesis of a wide variety of tertiary and quaternary nitriles, including examples where we successively and successfully added three different substituents on the carbon α to the nitrile. This method is generally applicable, high yielding and much greener than existing methods, and it has considerable advantages for industrial application.
Enantioselective Palladium-Catalyzed Oxidative Cascade Cyclization of Aliphatic Alkenyl Amides
Du, Wei,Gu, Qiangshuai,Li, Yang,Lin, Zhenyang,Yang, Dan
supporting information, p. 316 - 319 (2017/04/21)
The catalyst system of Pd(TFA)2/(S,S)-diPh-pyrox is reported to promote the highly efficient enantioselective oxidative cascade cyclization of alkene-tethered aliphatic acrylamides under mild aerobic conditions. A series of pyrrolizidine derivatives have been synthesized in good yield and excellent enantioselectivity. Deuterium-labeling experiments have revealed that the reaction proceeded through an anti-aminopalladation (anti-AP) pathway with high selectivity. The transition states for the anti-AP step have been calculated to account for the observed enantioselectivity.
Retro-Claisen benzylation: Direct use of benzyl alcohols in Pd-catalyzed couplings with nitriles
Maji, Tapan,Ramakumar, Kinthada,Tunge, Jon A.
supporting information, p. 14045 - 14048 (2015/02/05)
A new strategy has been developed for the benzylation of nitriles directly from benzyl alcohols. In this process benzyl alcohols undergo retro-Claisen activation with cyanoacetic esters to generate an active electrophile and a carbanionic nucleophile. In the presence of Pd(0) these intermediates undergo catalytic coupling to generate a new C - C bond, resulting in the formation of phenyl propionitriles.
Catalytic α-monoallylation of aryl acetonitriles
Maji, Tapan,Tunge, Jon A.
, p. 5072 - 5075 (2014/12/11)
α-Cyano aldehydes undergo selective transition-metal-catalyzed monoallylation to provide α-allylated nitriles. The transformation leads to linear substitution products with palladium catalysts or branched allylated nitriles using an iridium catalyst. Faci
Deacylative allylation: Allylic alkylation via retro-Claisen activation
Grenning, Alexander J.,Tunge, Jon A.
scheme or table, p. 14785 - 14794 (2011/11/04)
A new method for allylic alkylation of a variety of relatively nonstabilized carbon nucleophiles is described herein. In this process of "deacylative allylation", the coupling partners, an allylic alcohol and a ketone pronucleophile, undergo in situ retro-Claisen activation to generate an allylic acetate and a carbanion. In the presence of palladium, these reactive intermediates undergo catalytic coupling to form a new C-C bond. In comparison to unimolecular decarboxylative allylation, a commonly utilized method for allylation of carbon anions, deacylative allylation is an intermolecular process. Moreover, deacylative allylation allows the direct coupling of readily available allylic alcohols. Lastly, the full utility of deacylative allylation is demonstrated by the rapid construction of a variety 1,6-heptadienes via 3-component couplings.
A new synthesis of pyrrolidines by way of an enantioselective Mannich/diastereoselective hydroamination reaction sequence
Baxter Vu, Jenny M.,Leighton, James L.
supporting information; experimental part, p. 4056 - 4059 (2011/09/21)
A new two-step synthesis of highly substituted pyrrolidines has been developed. Chiral silane Lewis acid promoted enantioselective Mannich reactions of silyl ketene imines with acylhydrazones may be used to access bishomoallylic benzoic hydrazides that in
