1745-18-2Relevant academic research and scientific papers
A novel copper (I) mediated, symmetrical coupling procedure for alkyl, aryl, benzyl, and thiophenyl dihalides
Johnson,Johnson, David K.,Ciavarri,Ciavarri, Jeffrey P.,Ishmael,Ishmael, Faoud T.,Schillinger,Schillinger, Kurt J.,Van Geel,Van Geel, Thomas A. P.,Stratton,Stratton, Stephen M.
, p. 8565 - 8568 (1995)
A comparative study of Li2CuCl4 vs. Li2CuCl2 mediated mono-coupling reactions of dihalide substrates with allylmagnesium bromide is reported. Higher yields were obtained with Li2CuCl3 and the following trends in halide reactivity were observed. Br > Cl for alkyl, aryl, and thiophenyl dihalides; and benzyl halide > phenyl halide. Utilizing these trends, a symmetrical coupling procedure for alkyl, aryl, benzyl, and thiophenyl dihalides, simply carried out by combining the dihalide with metallic magnesium and Li2CuCl4 is reported.
MIDA boronate allylation-synthesis of ibuprofen
Brodie, Glen,France, David J.,Memarzadeh, Sarah,Phillips, David,Tang, Gi Lum
, p. 30624 - 30630 (2020/09/11)
MIDA boronates are among the most useful reagents for the Suzuki-Miyaura reaction. This chemistry typically generates new bonds between two aromatic rings, thereby restricting access to important areas of chemical space. Here we demonstrate the coupling of MIDA boronates to allylic electrophiles, including a new synthesis of the well-known COX inhibitor ibuprofen. This journal is
Manganese catalyzed dehydrogenative silylation of alkenes: Direct access to allylsilanes
Wu, Shang,Zhang, Ying,Jiang, Hongyan,Ding, Ning,Wang, Yanbin,Su, Qiong,Zhang, Hong,Wu, Lan,Yang, Quanlu
supporting information, (2020/06/03)
Dehydrogenative silylation of alkenes with silanes to produce allylsilanes is achieved through manganese catalysis with a wide scope of substrate tolerance. This transformation involves silane radicals initiated by manganese complex without additional oxidant additives. It offers a general, convenient and practical protocol with excellent functional group compatibility and gram-scale capacity for the modular synthesis of allylsilanes.
Palladium-Catalyzed Oxidative Allylation of Sulfoxonium Ylides: Regioselective Synthesis of Conjugated Dienones
Li, Chunsheng,Li, Meng,Zhong, Wentao,Jin, Yangbin,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 872 - 875 (2019/05/16)
The first examples of palladium-catalyzed allylic C-H oxidative allylation of sulfoxonium ylides to afford the corresponding conjugated dienones with moderate to good yields have been established. The features of this novel conversion include mild reaction conditions, wide substrate scope, and excellent regioselectivity.
Palladium-catalyzed tandem isomerization/hydrothiolation of allylarenes
Kathe, Prasad M.,Fleischer, Ivana
supporting information, p. 2213 - 2217 (2019/03/26)
Herein we report a tandem olefin migration/hydrothiolation of allyl benzenes facilitated by an in situ generated palladium hydride. A catalyst system composed of palladium acetate and bidentate ligand dtbpx (1,2-bis(di-tert-butylphosphinomethyl)benzene in the presence of catalytic amounts of triflic acid led to the tandem transformation, which furnished benzylic thioethers. The reaction exhibits high regioselectivity and can be conducted under mild conditions. The robustness of the catalyst is displayed through reactions with coordinating thiols.
Palladium-catalyzed allylic C-H oxidation under simple operation and mild conditions
Guo, Yunlong,Shen, Zengming
supporting information, p. 3103 - 3107 (2019/03/26)
We discovered an effective and simple system (Pd/BQ/air/r.t.) for making allylic alcohols through Pd-catalyzed allylic C-H bond functionalization. This approach exhibits advantages due to its simple operation, mild conditions, and environmentally benign features. By modifying reaction conditions, it can be suitable for preparing unsaturated aldehydes, allylic esters, ethers, and amines.
Cross-Coupling Reactions of Aryldiazonium Salts with Allylsilanes under Merged Gold/Visible-Light Photoredox Catalysis
Akram, Manjur O.,Mali, Pramod S.,Patil, Nitin T.
supporting information, p. 3075 - 3078 (2017/06/23)
A method for the cross-coupling reactions of aryldiazonium salts with trialkylallylsilanes via merged gold/photoredox catalysis is described. The reaction is proposed to proceed through a photoredox-promoted generation of an electrophilic arylgold(III) intermediate that undergoes transmetalation with allyltrimethylsilane to form allylarenes.
Palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane: Synthesis of homoallylic boronic esters
Li, Chunsheng,Li, Meng,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 66 - 69 (2017/12/27)
A palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane to afford the corresponding homoallylic organoboronic esters with moderate to excellent yields is reported. This novel transformation provides an efficient strategy for the construction of homoallylic organoboronic esters in one step with a broad substrate scope. It is proposed that the palladium-catalyzed oxidative allylic C-H bond activation process may be involved in the catalytic cycle.
Anti-Markovnikov rearrangement in sulfur mediated allylic C-H amination of olefins
Zhang, Zhong,Du, Hongguang,Xu, Jiaxi,Li, Pingfan
supporting information, p. 11547 - 11550 (2016/10/03)
Cationic rearrangement reactions usually follow Markovnikov's rule to give more substituted carbocations as stable intermediates. During our study on sulfur mediated allylic C-H amination of olefins, very rare cases of anti-Markovnikov rearrangement from secondary carbocations toward primary carbocations or primary triflates were observed.
Palladium-catalyzed aerobic oxidative double allylic C-H oxygenation of alkenes: A novel and straightforward route to α,β-unsaturated esters
Yang, Wanfei,Chen, Huoji,Li, Jianxiao,Li, Chunsheng,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 9575 - 9578 (2015/06/08)
A mild tandem oxidative functionalization of allyl aromatic hydrocarbons was accomplished using the catalytic system of Pd(OAc)2/DMA under 1 atm O2. The green twofold C-O bond formation involving double allylic C-H oxygenation unlocks opportunities for markedly different synthetic strategies. Moreover, the reaction affords aryl α,β-unsaturated esters directly from readily available terminal olefins in moderate to good yields with excellent chemo- and stereoselectivities.
