1163708-25-5Relevant articles and documents
Photoinduced Deaminative Borylation of Unreactive Aromatic Amines Enhanced by CO2
Shiozuka, Akira,Sekine, Kohei,Kuninobu, Yoichiro
, p. 4774 - 4778 (2021/06/28)
Herein, direct unreactive C-N borylation of aromatic amines by a photocatalyst was achieved. The C-N borylation of aromatic amines with bis(pinacolato)diboron (B2pin2) proceeded using a pyrene catalyst under light irradiation to afford desired borylated products and aminoborane as a byproduct. The yield of the borylated product improved under a CO2 atmosphere which probably reduced the inhibitory effect of aminoborane. Mechanistic studies suggested that the C-N bond cleavage and C-B bond formation proceeded via a concerted pathway.
DFT-Guided Phosphoric-Acid-Catalyzed Atroposelective Arene Functionalization of Nitrosonaphthalene
Ding, Wei-Yi,Yu, Peiyuan,An, Qian-Jin,Bay, Katherine L.,Xiang, Shao-Hua,Li, Shaoyu,Chen, Ying,Houk,Tan, Bin
supporting information, p. 2046 - 2059 (2020/07/13)
Guided by computational design, Tan and colleagues disclose a chiral phosphoric-acid-catalyzed asymmetric functionalization of naphthalenes with nitroso as the activating and directing group. This nucleophilic aromatic substitution reaction allows divergent access to two types of axially chiral arylindole frameworks with wide substrate generality under excellent enantiocontrol and, more importantly, offers a facile approach to the privileged NOBIN (2-amino-2′-hydroxy-1,1′-binaphthyl) structures. DFT calculations illustrate the plausible reaction pathway and provide additional insights into the origins of enantioselectivity.Functionalization of arenes represents the most efficient approach for constructing a core backbone of important aryl compounds. Compared with the well-developed electrophilic aromatic substitution and transition-metal-catalyzed C–H activation, nucleophilic aromatic substitution remains challenging because of the lack of a convenient route for rapid conversion of the σH adduct to other stable and versatile intermediates in situ. Guided by computational design, we were able to realize asymmetric nucleophilic aromatic substitution by introducing a nitroso group on naphthalene via chiral phosphoric acid catalysis. This strategy enables efficient construction of atropisomeric indole-naphthalenes and indole-anilines with excellent stereocontrol. Density functional theory (DFT) calculations provide further insights into the origins of enantioselectivity and the reaction mechanisms. The successful application in the synthesis of NOBINs (2-amino-2′-hydroxy-1,1′-binaphthyl) extends the utility of this strategy.Highly efficient conversion of inexpensive and readily available arene materials into high-value-added chiral molecules is of great importance in modern synthetic chemistry given the enormous potential of such structures in functional materials, pharmaceuticals, and other relevant chemical industries. Organocatalytic nucleophilic aromatic substitution enabled by an azo group offers an effective approach to enantioselective functionalization of naphthalene C–H bonds featuring an intramolecular oxidation of an unstabilized σH adduct. Premised on density functional theory (DFT) calculations, nitroso has emerged as another promising activating and oxidative group, whose synthetic potential is substantiated in the atroposelective synthesis of several groups of representative biaryl atropisomers processed by a chiral phosphoric acid catalyst. The success of this reaction explicitly exemplifies the ability of computational tools to streamline organic synthesis with intensified robustness in the disclosed strategy.
Synthesis of Styrenes by Palladium(II)-Catalyzed Vinylation of Arylboronic Acids and Aryltrifluoroborates by Using Vinyl Acetate
Lindh, Jonas,Saevmarker, Jonas,Nilsson, Peter,Sjoeberg, Per J. R.,Larhed, Mats
supporting information; experimental part, p. 4630 - 4636 (2009/12/26)
Reactions of aromatic and heteroaromatic boronic acids or aryltrifluoroborate salts with vinyl acetate in the presence of a palladium(II) catalyst give the corresponding styrenes in good yields. This Heck reaction proceeds with microwave heating in less t
