52267-15-9Relevant academic research and scientific papers
Dual Nickel- And Photoredox-Catalyzed Reductive Cross-Coupling of Aryl Halides with Dichloromethane via a Radical Process
Xu, Tao,Xu, Wenhao,Zheng, Purui
supporting information, (2020/11/13)
The first catalytic strategy to harness a new chloromethane radical from dichloromethane under dual Ni/photoredox catalytic conditions has been developed. Compared with traditional two-electron reductive process associated with metallic reductants, this method via a single-electron approach can proceed under exceptionally mild conditions (visible light, ambient temperature, no strong base) and exhibits complementary reactivity patterns. It affords a broad scope of many functional groups, including alkenyl, which suffers cyclopropanation in previous routes. The diarylmethane-d2 compounds can be readily available with this transformation.
Nickel-Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents
Wang, Gaonan,Gan, Yi,Liu, Yuanhong
supporting information, p. 916 - 920 (2018/09/22)
The direct coupling of allylic alcohols with arylboronic acids or their derivatives catalyzed by Ni(cod)2 in the presence of a catalytic amount of base has been developed. A wide variety of allylic substrates or arylboronic acids turned out to be applicable to this catalytic system. The present method does not require the use of ligands for stabilizing the nickel catalyst in most cases or additional activators for activation of allylic alcohols.
One-pot Synthesis of 1,3-Butadiene and 1,6-Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions
Turczel, Gábor,Kovács, Ervin,Csizmadia, Eszter,Nagy, Tibor,Tóth, Imre,Tuba, Robert
, p. 4884 - 4891 (2018/09/25)
A novel tandem reaction of cyclopentadiene leading to high value linear chemicals via ruthenium catalyzed ring opening cross metathesis (ROCM), followed by cross metathesis (CM) is reported. The ROCM of cyclopentadiene (CPD) with ethylene using commercially available 2nd gen. Grubbs metathesis catalysts (1-G2) gives 1,3-butadiene (BD) and 1,4-pentadiene (2) (and 1,4-cyclohexadiene (3)) with reasonable yields (up to 24 % (BD) and 67 % (2+3) at 73 % CPD conversion) at 1–5 mol % catalyst loading in toluene solution (5 V% CPD, 10 bar, RT) in an equilibrium reaction. The ROCM of CPD with cis-butene diol diacetate (4) using 1.00 - 0.05 mol % of 3rd gen. Grubbs (1-G3) or 2nd gen. Hoveyda-Grubbs (1-HG2) catalysts loading gives hexa-2,4-diene-1,6-diyl diacetate (5), which is a precursor of 1,6-hexanediol (an intermediate in polyurethane, polyester and polyol synthesis) and hepta-2,5-diene-1,7-diyl diacetate (6) in good yield (up to 68 % or TON: 1180). Thus, convenient and selective synthetic procedures are revealed by ROCM of CPD with ethylene and 4 leading to BD and 1,6-hexanediol precursor, respectively, as key components of commercial intermediates of high-performance materials.
CaII-Catalyzed Alkenylation of Alcohols with Vinylboronic Acids
Leb?uf, David,Presset, Marc,Michelet, Bastien,Bour, Christophe,Bezzenine-Lafollée, Sophie,Gandon, Vincent
supporting information, p. 11001 - 11005 (2015/11/10)
Direct alkenylation of a variety of alcohols with vinylboronic acids has been accomplished using the air-stable calcium(II) complex Ca(NTf2)2 under mild conditions with short reaction times. For reluctant transformations, an ammonium salt was used as an additive to circumvent the reactivity issue. Cross-coupling: Direct alkenylation of a variety of alcohols with vinylboronic acids has been accomplished using the air-stable calcium(II) complex Ca(NTf2)2 under mild conditions with short reaction times (see scheme)
Catalyst-controlled reverse selectivity in C-C bond formation: NHC-Cu-catalyzed α-selective allylic alkylation with organolithium reagents
Pizzolato, Stefano F.,Giannerini, Massimo,Bos, Pieter H.,Fa?anás-Mastral, Martín,Feringa, Ben L.
supporting information, p. 8142 - 8145 (2015/05/20)
An efficient and highly α-selective copper-catalyzed allylic alkylation of allylic halides with organolithium reagents is presented. The use of N-heterocyclic carbenes as ligands is key to reverse the common γ-selectivity of this transformation and gives rise to the corresponding linear products with high levels of regioselectivity.
Dehydrative cross-coupling reactions of allylic alcohols with olefins
Gumrukcu, Yasemin,De Bruin, Bas,Reek, Joost N. H.
supporting information, p. 10905 - 10909 (2014/09/17)
The direct dehydrative activation of allylic alcohols and subsequent cross-coupling with alkenes by using palladium catalyst containing a phosphoramidite ligand is described. The activation of the allyl alcohol does not require stoichiometric additives, thus allowing clean, waste-free reactions. The scope is demonstrated by application of the protocol to a series allylic alcohols and vinyl arenes, leading to variety of 1,4-diene products. Based on kinetic studies, a mechanism is proposed that involves a palladium hydride species that activates the allyl alcohol to form the allyl intermediate.
Iridium-catalyzed enantioselective allylic vinylation
Hamilton, James Y.,Sarlah, David,Carreira, Erick M.
supporting information, p. 994 - 997 (2013/04/10)
The first example of Ir-catalyzed asymmetric substitution reaction with vinyl trifluoroborates is described. The direct reaction between branched, racemic allylic alcohols and potassium alkenyltrifluoroborates proceeded with high site selectivity and exce
Facile coupling of propargylic, allylic and benzylic alcohols with allylsilane and alkynylsilane, and their deoxygenation with Et3SiH, catalyzed by Bi(OTf)3 in [BMIM][BF4] ionic liquid (IL), with recycling and reuse of the IL
Narayana Kumar,Laali, Kenneth K.
experimental part, p. 7347 - 7355 (2012/09/25)
Allyltrimethylsilane (allyl-TMS) reacts with propargylic alcohols 1a-1d in the presence of 10% Bi(OTf)3 in [BMIM][BF4] solvent to furnish the corresponding 1,5-enynes in respectable isolated yields (87-93%) at room temperature. The utility of Bi(OTf)3 as a superior catalyst was demonstrated in a survey study on coupling of allyl-TMS with 1a employing several metallic triflates (Bi, Ln, Al, Yb) as well as, B(C6F 5)3, Zn(NTf2)2 and Bi(NO 3)3·5H2O. Coupling of cyclopropyl substituted propargylic alcohol 1e with allyl-TMS gave the skeletally intact 1,5-enyne and a ring opened derivative as a mixture. Coupling of propargylic/allylic alcohol 1f with allyl-TMS resulted in allylation at both benzylic (2 isomers) and propargylic positions, as major and minor products respectively. The scope of this methodology for allylation of a series of allylic and benzylic alcohols was explored. Chemoselective reduction of a host of propargylic, propagylic/allylic, bis-allylic, allylic, and benzylic alcohols with Et3SiH was achieved in high yields with short reaction times. The same approach was successfully applied to couple representative propargylic and allylic alcohols with 1-phenyl-2-trimethylsilylacetylene. The recovery and reuse of the ionic liquid (IL) was gauged in a case study with minimal decrease in isolated yields after six cycles.
Regioselective and stereospecific cross-coupling of primary allylic amines with boronic acids and boronates through palladium-catalyzed C-N bond cleavage
Li, Man-Bo,Wang, Yong,Tian, Shi-Kai
supporting information; experimental part, p. 2968 - 2971 (2012/04/18)
The NH2 group serves as an effective leaving group in the palladium-catalyzed regioselective and stereospecific title reaction (see scheme). The reaction works well with aryl- and alkenylboronic acids and aryl-, alkenyl-, allyl-, and benzylboronates, and complete transfer of chirality has been achieved when using α-chiral primary allylic amines as the allylic electrophiles. Copyright
Palladium-catalyzed cross-coupling reactions of organogold(i) phosphanes with allylic electrophiles
Pena-Lopez, Miguel,Ayan-Varela, Miguel,Sarandeses, Luis A.,Sestelo, Jose Perez
experimental part, p. 1686 - 1694 (2012/03/22)
Aryl and alkenylgold(i) phosphanes react regioselectively with allylic electrophiles such as cinnamyl and geranyl halides (bromide, chloride and acetates) under palladium catalysis in THF at 80 °C to afford the α-substitution product with moderate to high yields. When the reaction is performed with a chiral enantiopure secondary acetate, the α-substituted cross-coupling product is obtained with complete inversion of the stereochemistry.
