210347-86-7Relevant academic research and scientific papers
Ligand-Controlled Regiodivergence for Catalytic Stereoselective Semireduction of Allenamides
Hajiloo Shayegan, Mojtaba,Li, Zhong-Yuan,Cui, Xin
, (2021/12/02)
Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo- and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3-semireduction, producing (E)-enamide derivatives.
Hydrosilylation and Mukaiyama aldol-type reaction of quinolines and hydrosilylation of imines catalyzed by a mesoionic carbene-stabilized borenium ion
Bestvater, Brian P.,Clarke, Joshua J.,Crudden, Cathleen M.,DeJesus, Joseph F.,Devaraj, Karthik,Eisenberger, Patrick,Kojima, Ryoto
supporting information, p. 6786 - 6791 (2021/08/20)
Aldimines and ketimines containing electron-donating and electron-withdrawing groups can be hydrosilylated with borenium catalysts at as low as 1 mol% catalyst loading at room temperature, providing the corresponding secondary amines in excellent yields. Reactions with 2-phenylquinoline gave the 1,4-hydrosilylquinoline product selectively which can be further functionalized in a one-pot synthesis to give unique γ-amino alcohol derivatives. Control experiments suggest that the borenium ion catalyzes both the hydrosilylation and subsequent addition to the aldehyde.
Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron-Rich Substrates
Doobary, Sayad,Sedikides, Alexi T.,Caldora, Henry P.,Poole, Darren L.,Lennox, Alastair J. J.
, p. 1155 - 1160 (2019/12/11)
Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene-types and tolerance of electron-rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene-types that is tolerant of electron-rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex-cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales.
A Next-Generation Air-Stable Palladium(I) Dimer Enables Olefin Migration and Selective C?C Coupling in Air
Kundu, Gourab,Rissanen, Kari,Schoenebeck, Franziska,Sperger, Theresa
, p. 21930 - 21934 (2020/10/02)
We report a new air-stable PdI dimer, [Pd(μ-I)(PCy2tBu)]2, which triggers E-selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C?C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C?Br, C?OTf/OFs, and C?Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous PdI dimer generations for substrates that bear substituents ortho to C?OTf.
Tert-Butyl Nitrite: Organic Redox Cocatalyst for Aerobic Aldehyde-Selective Wacker-Tsuji Oxidation
Ning, Xiao-Shan,Wang, Mei-Mei,Yao, Chuan-Zhi,Chen, Xian-Min,Kang, Yan-Biao
, p. 2700 - 2703 (2016/06/15)
An aldehyde-selective aerobic Wacker-Tsuji oxidation is developed. Using tert-butyl nitrite as a simple organic redox cocatalyst instead of copper or silver salts, a variety of aldehydes were achieved as major products in up to 30/1 regioselectivity as well as good to high yields at room temperature.
Palladium-Catalyzed Allylic Amination of Homoallylic Alcohols with Amines via Carbon-Carbon Bond Cleavage
Sun, Gui-Jun,Wang, Yong,Kang, Qiang
, p. 2931 - 2936 (2015/09/28)
An efficient approach for palladium(II) acetate catalyzed allylic amination of homoallylic alcohols with various amines via sequential retro-allylation and amination was developed, which afforded the corresponding allylic amines in up to 98% yield.
Copper-catalyzed trifluoromethylation and cyclization of aromatic-sulfonyl-group-tethered alkenes for the construction of 1,2-benzothiazinane dioxide type compounds
Dong, Xiang,Sang, Rui,Wang, Qiang,Tang, Xiang-Ying,Shi, Min
, p. 16910 - 16915 (2014/01/06)
A multi-talented system: An efficient copper-catalyzed tandem trifluoromethylation/annulation of an electron-deficient aromatic ring has been developed. This method provides a powerful and straightforward way to synthesize trifluoromethylated 1,2-benzothiazinane dioxides under mild conditions (see scheme). The mechanism was investigated by a series of kinetic experiments and isotopic labeling studies.
