15463-92-0Relevant articles and documents
Room-temperature Pd-catalyzed methoxycarbonylation of terminal alkynes with high branched selectivity enabled by bisphosphine-picolinamide ligand
Chen, Fen-Er,Ke, Miaolin,Liu, Ding,Ning, Yingtang,Ru, Tong
supporting information, p. 1041 - 1044 (2022/01/28)
We report the room-temperature Pd-catalyzed methoxy-carbonylation with high branched selectivity using a new class of bisphosphine-picolinamide ligands. Systematic optimization of ligand structures and reaction conditions revealed the significance of both
Palladium-Catalyzed Asymmetric Hydroesterification of α-Aryl Acrylic Acids to Chiral Substituted Succinates
Ji, Xiaolei,Shen, Chaoren,Tian, Xinxin,Dong, Kaiwu
supporting information, p. 8645 - 8649 (2021/10/25)
A palladium-catalyzed asymmetric hydroesterification of α-aryl acrylic acids with CO and alcohol was developed, preparing a variety of chiral α-substituted succinates in moderate yields with high ee values. The kinetic profile of the reaction progress revealed that the alkene substrate first underwent the hydroesterification followed by esterification with alcohol. The origin of the enantioselectivity was elucidated by density functional theory computation.
Stereoconvergent Reduction of Activated Alkenes by a Nicotinamide Free Synergistic Photobiocatalytic System
Wang, Yajie,Huang, Xiaoqiang,Hui, Jingshu,Vo, Lam Tung,Zhao, Huimin
, p. 9431 - 9437 (2020/10/06)
There is a growing interest in developing cooperative chemoenzymatic reactions to harness the reactivity of chemical catalysts and the selectivity of enzymes for the synthesis of nonracemic chiral compounds. However, existing chemoenzymatic systems with m
Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli-responsive Li+-enriched Metallogel Formation
Dixit, Manish K.,Dubey, Mrigendra,Kalam, Abul,Kumar, Yeeshu,Mahendar, Chinthakuntla,Sharma, Vinay K.,Shukla, Jay
, p. 3020 - 3028 (2020/09/04)
A fluorescent metallogel (2.6 % w/v) has been obtained from two non-fluorescent components viz. phenyl-succinic acid derived pro-ligand H2PSL and LiOH (2 equiv.) in DMF. Li+ ion not only plays a crucial role in gelation through aggre
Synergetic Catalysis for One-pot Bis-alkoxycarbonylation of Terminal Alkynes over Pd/Xantphos?Al(OTf)3 Bi-functional Catalytic System
Guo, Wen-Di,Liu, Lei,Yang, Shu-Qing,Chen, Xiao-Chao,Lu, Yong,VO-Thanh, Giang,Liu, Ye
, p. 1376 - 1384 (2020/01/24)
Tandem bis-alkoxycarbonylation of alkynes allows for the preparation of 2-substituted succinates from alkynes and nucleophile alcohol via two successive alkoxycarbonylation with advantages of 100 % atomic economy and simplified one-pot operation. Herein, the one-pot tandem bis-alkoxycarbonylation of alkynes was accomplished over the bi-functional catalytic system containing Xantphos-modified Pd-complex and Lewis super-acid of Al(OTf)3. It was found that, via the synergetic catalysis, the involved Xantphos-modified Pd-complex was responsible for the activation of CO and the alkynes through coordination to Pd-center while Al(OTf)3 was in charge of the activation of the alcohol to facilitate the formation of [Pd?H]+ active species. The in situ high-pressure FT-IR analysis, coupled with 1H/13C NMR spectral characterizations, confirmed that the introduced Al(OTf)3 with intensive oxophilicity (via acid-base pair interaction) was able to activate nucleophilic MeOH to be a reliable proton-donor (i. e. hydride-source) to warrant the formation and stability of [Pd?H]+ species upon the oxidation of Pd0 by H+ (Pd0+H+→[PdII?H]+). Over the developed bi-functional catalytic system, the yields of the target diesters were obtained in the range of 36～86 % in this sequence with the wide substrate scope.
Diversion of the Arbuzov reaction: Alkylation of C-Cl instead of phosphonic ester formation on the fullerene cage
Kraevaya, Ol'Ga A.,Peregudov, Alexander S.,Troyanov, Sergey I.,Godovikov, Ivan,Fedorova, Natalya E.,Klimova, Regina R.,Sergeeva, Vasilina A.,Kameneva, Larisa V.,Ershova, Elizaveta S.,Martynenko, Vyacheslav M.,Claes, Sandra,Kushch, Alla A.,Kostyuk, Svetlana V.,Schols, Dominique,Shestakov, Alexander F.,Troshin, Pavel A.
supporting information, p. 7155 - 7160 (2019/08/07)
We report an "inversed" Arbuzov reaction of the fullerene derivatives C60Ar5Cl with trialkyl phosphites P(OR)3 producing alkylated fullerene derivatives C60Ar5R (R = Me, Et, iPr, nBu) with almost quantitative yields. This reaction provides a convenient synthetic route for the preparation of a large variety of functionalized fullerene derivatives with tailored properties, e.g. water-soluble compounds demonstrating promising antiviral activities against HCMV, HSV1, HIV and several influenza virus strains.
Selective Palladium-Catalyzed Carbonylation of Alkynes: An Atom-Economic Synthesis of 1,4-Dicarboxylic Acid Diesters
Liu, Jiawang,Dong, Kaiwu,Franke, Robert,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
, p. 10282 - 10288 (2018/08/03)
A class of novel diphosphine ligands bearing pyridine substituents was designed and synthesized for the first time. The resulting palladium complexes of L1 allow for chemo- and regioselective dialkoxycarbonylation of various aromatic and aliphatic alkynes affording a wide range of 1,4-dicarboxylic acid diesters in high yields and selectivities. Kinetic studies suggest the generation of 1,4-dicarboxylic acid diesters via cascade hydroesterification of the corresponding alkynes. Based on these investigations, the chemo- and regioselectivities of alkyne carbonylations can be controlled as shown by switching the ligand from L1 to L3 or L9 to give α,β-unsaturated esters.
Co-catalysis over a bi-functional ligand-based Pd-catalyst for tandem bis-alkoxycarbonylation of terminal alkynes
Yang, Da,Liu, Huan,Wang, Dong-Liang,Luo, Zhoujie,Lu, Yong,Xia, Fei,Liu, Ye
supporting information, p. 2588 - 2595 (2018/06/11)
A bi-functional ligand (L1) containing a diphosphino fragment and sulfonic acid group (-SO3H) enabled PdCl2(MeCN)2 to efficiently catalyze the tandem bis-alkoxycarbonylation of terminal alkynes to produce aryl-/alkyl-substituted succinate (α,ω-diesters). It was found that the -SO3H incorporated in L1 indispensably assisted the Pd-catalyst in accomplishing this tandem reaction via intramolecular synergic effects. Co-catalysis over the L1-based Pd-catalyst was not due to the physical mixture of Xantphos and MeSO3H. In situ FTIR analysis verified that the formation and stability of Pd-H active species were facilitated by the presence of L1. The formation of stabilized diacylpalladium intermediate (F) was the critical driving force for the second-step methoxycarbonylation. DFT calculation was carried out to optimize the geometric structure of F, which indicated that the developed intramolecular O?H hydrogen bonds were an important structural feature to stabilize F. In addition, the L1-based Pd-catalyst could be recycled successfully for at least 3 runs in the ionic liquid [Bmim]NTf2 without obvious activity loss and detectable metal leaching.
Autoinductive conversion of α,α-diiodonitroalkanes to amides and esters catalysed by iodine byproducts under O2
Li, Jing,Lear, Martin J.,Hayashi, Yujiro
supporting information, p. 6360 - 6363 (2018/06/21)
Studies to convert nitroalkanes into amides and esters using I2 and O2 revealed in situ-generated iodine species facilitate the homolytic C-I bond cleavage of α,α-diiodonitroalkanes, arguably in an autoinductive or autocatalytic manner. Consequently, we devised a rapid and economical I2/O2-based method to synthesise sterically hindered esters directly from primary nitroalkanes.
Development of efficient palladium catalysts for alkoxycarbonylation of alkenes
Liu, Jiawang,Dong, Kaiwu,Franke, Robert,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
supporting information, p. 12238 - 12241 (2018/11/21)
Herein, we report a general and efficient Pd-catalysed alkoxycarbonylation of sterically hindered and demanding olefins including a variety of tri-, tetra-substituted and 1,1-disubstituted alkenes. In the presence of 1,3-bis(tert-butyl(pyridin-2-yl)phosphanyl)propane L3 or 1,4-bis(tert-butyl(pyridin-2-yl)phosphanyl)butane L4 the desired esters are obtained in good yields and selectivities. Similar transformation is obtained using tertiary ether as showcased in the carbonylation of MTBE to the corresponding linear ester in high yield and selectivity.
