- Arylketones as Aryl Donors in Palladium-Catalyzed Suzuki-Miyaura Couplings
-
Herein, we report the arylation, alkylation, and alkenylation of aryl ketones via a palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. The use of the pyridine-oxazoline ligand is the key to the cleavage of the unstrained C-C bond. The late-stage arylation of aryl ketones derived from drugs and natural products demonstrated the synthetic utility of this protocol.
- Wang, Zhen-Yu,Ma, Biao,Xu, Hui,Wang, Xing,Zhang, Xu,Dai, Hui-Xiong
-
p. 8291 - 8295
(2021/11/13)
-
- Selective Conversion of Benzylic Phosphates into Diarylmethanes Through Al(OTf)3-Catalyzed Friedel–Crafts-Type Benzylation
-
Al(OTf)3 was identified as a high-performance catalyst for Friedel–Crafts-type benzylation using benzylic phosphates as electrophiles. The reaction proceeded even with 0.2 mol-% of the catalyst. A series of diarylmethanes (21 examples) was obtained in moderate to high yield. The catalyst showed unique chemoselectivity, preferentially converting the benzylic phosphate motif, even with a benzylic acetate group existed in the same molecule.
- Yurino, Taiga,Hachiya, Asuka,Suzuki, Keisuke,Ohkuma, Takeshi
-
p. 2225 - 2232
(2020/04/16)
-
- One-pot reductive coupling reactions of acetyl naphthalene derivatives, tosylhydrazide, with arylboronic acids
-
In this study, a one-pot two-step reductive coupling between acetyl naphthalene derivatives, tosylhydrazide, and arylboronic acids, affording substituted 1(or 2)-(1-phenylethyl)naphthalenes in moderate-to-excellent yields, was reported. Notably, solvent played a crucial role in the coupling of 1-acetyl naphthalene derivatives (toluene) or 2-acetyl naphthalene derivatives (1,4-dioxane) as starting materials. Meanwhile, the scope of this one-pot coupling reaction was extended to 1(or 2)-naphthaldehyde substrates. Particularly, the system was also suitable to synthesize 1(or 2)-(1-phenylethyl)naphthalenes on a multi-gram scale, and was applied in the synthesis of naphthylmethyl substituted carbazolyl compounds.
- Shen, Xu,Liu, Ping,Liu, Yang,Liu, Yan,Dai, Bin
-
supporting information
p. 785 - 793
(2017/01/16)
-
- Synthetic method of diarylmethanes
-
The invention discloses a synthetic method of diarylmethanes. The method is characterized in that benzyl pseudohalide and aromatic boric acid are reacted in an organic solvent under alkaline condition. The method employs easily available raw materials, conversion is realized under effect of no transition metal catalysis, water-free and oxygen-free are not required, Lewis acid catalysis is not required, the method has wide substrate universality, and various substituted diarylmethanes can be synthesized by the method.
- -
-
Paragraph 0066; 0067; 0068; 0069; 0070
(2017/08/28)
-
- Practical Cross-Coupling between O-Based Electrophiles and Aryl Bromides via Ni Catalysis
-
Cross-coupling of various O-based electrophiles with aryl bromides was developed through Ni-catalyzed C-O activation in the presence of magnesium. Beside carboxylates, carbamates, and ethers, phenols exhibited excellent reactivity under modified conditions. This chemistry was featured as a simple and environmentally benign process with low catalyst loading and easy manipulations. The method exhibited broad substrate scopes.
- Cao, Zhi-Chao,Luo, Qin-Yu,Shi, Zhang-Jie
-
supporting information
p. 5978 - 5981
(2016/12/09)
-
- Coupling of arylboronic acids with benzyl halides or mesylates without adding transition metal catalysts
-
We report herein a transition-metal-free coupling reaction of arylboronic acids with benzyl halides and mesylates for the construction of C(sp2)[sbnd]C(sp3) bonds. A unique feature of this coupling reaction is the formation regioisomers in some cases. Mechanistic studies suggest that this reaction may proceed via an unprecedented Friedel–Crafts-type reaction pathway under base conditions with the assistance of boronic acid moiety.
- Wu, Guojiao,Xu, Shuai,Deng, Yifan,Wu, Chaoqiang,Zhao, Xia,Ji, Wenzhi,Zhang, Yan,Wang, Jianbo
-
p. 8022 - 8030
(2016/11/19)
-
- Nickel/N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Type Cross-Coupling of Aryl Carbamates
-
The utility of N-heterocyclic carbene ligands in nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl esters and carbamates is investigated. Imidazol-2-ylidene bearing 2-adamantyl groups at its nitrogen atoms generates the most active nickel species among the ligands examined, allowing cross-coupling of a range of aryl carbamates and pivalates. Unlike the previously reported system using tricyclohexylphosphine, this protocol is suitable for the cross-coupling using arylboronic esters in addition to arylboronic acids.
- Ohtsuki, Akimichi,Yanagisawa, Kousuke,Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
-
p. 9409 - 9414
(2016/10/17)
-
- Intra- and Intermolecular Nickel-Catalyzed Reductive Cross-Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides
-
Nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides have been developed. Both inter- and intramolecular variants proceed under mild reaction conditions. A range of heterocycles and functional groups are tolerated under the reaction conditions. Additionally, the first example of a stereospecific cross-electrophile coupling of a secondary benzylic ester is described. Crossed off: Nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides have been developed. Both inter- and intramolecular variants proceed under mild reaction conditions, and a range of heterocycles and functional groups are tolerated. Additionally, the first example of a stereospecific cross-electrophile coupling of a secondary benzylic ester is described.
- Konev, Mikhail O.,Hanna, Luke E.,Jarvo, Elizabeth R.
-
supporting information
p. 6730 - 6733
(2016/06/09)
-
- Direct cross-coupling of benzyl alcohols to construct diarylmethanes via palladium catalysis
-
A direct arylation to furnish diarylmethanes from benzyl alcohols was realized through Pd(PPh3)4-catalyzed Suzuki-Miyaura coupling via benzylic C-O activation in the absence of any additives. The arylation is compatible with various functional groups. This development provides an atom- and step-economic way to approach a diarylmethane scaffold under mild and environmentally benign conditions. This journal is
- Cao, Zhi-Chao,Yu, Da-Gang,Zhu, Ru-Yi,Wei, Jiang-Bo,Shi, Zhang-Jie
-
supporting information
p. 2683 - 2686
(2015/03/05)
-
- Iridium-catalyzed diborylation of benzylic C-H bonds directed by a hydrosilyl group: Synthesis of 1,1-benzyldiboronate esters
-
We describe a regioselective diborylation of primary benzylic C-H bonds catalyzed by [Ir(COD)OMe]2 and 4,4′-di-tert-butyl-2,2′- bipyridine (dtbpy). The hydrosilyl group acts as a traceless directing group, providing access to a range of 1,1-benzyldiboronate esters in good yields. Transformations of the 1,1-benzyldiboronate ester products include chemoselective Suzuki-Miyaura cross-couplings and synthesis of tetrasubstituted alkenyl boronate esters.
- Cho, Seung Hwan,Hartwig, John F.
-
p. 694 - 698
(2014/01/17)
-
- Tin exchanged heteropoly tungstate: An efficient catalyst for benzylation of arenes with benzyl alcohol
-
The partial exchange of tin with the protons of 12-tungstophosphoric acid (TPA) results in a highly active heterogeneous catalyst for benzylation of arenes with benzyl alcohol as benzylating agent. The catalysts were characterized by X-ray diffraction, Laser-Raman and FT-IR of pyridine adsorption. The catalytic activity depends significantly on the extent of tin exchanged with the protons of heteropoly tungstate. The characterization results suggest the presence of Lewis acidic sites by the exchange of tin. The catalyst with partial exchange of Sn showed high benzylation activity, which in turn related to variation in acidity of the catalysts. The catalyst is highly active for benzylation reaction irrespective of the nature of substituted arenes and benzyl alcohols. These catalysts are highly active compared to other acid catalysts used for benzylation of different arenes. The catalyst is easy to separate from reaction mixture and exhibit consistent activity upon reuse. The plausible reaction mechanism based on the role of both Lewis and Bronsted acid sites of the catalyst was discussed.
- Ramesh Kumar, Ch.,Rao, K.T. Venkateswara,Sai Prasad,Lingaiah
-
experimental part
p. 17 - 24
(2011/04/21)
-
- Nickel-catalyzed alkenylative cross-coupling reaction of alkyl sulfides
-
A novel cross-coupling reaction of alkyl aryl sulfides with aryl Grignard reagents has been achieved to produce the alkenyl-aryl coupling products in high yields by using catalytic Ni(cod)2 and a bulky N-heterocyclic carbene ligand, SIPr.
- Ishizuka, Kentaro,Seike, Hirofumi,Hatakeyama, Takuji,Nakamura, Masaharu
-
scheme or table
p. 13117 - 13119
(2010/11/05)
-
- Efficient and selective alkylation of arenes and heteroarenes with benzyl and allyl ethers using a Ir/Sn bimetallic catalyst
-
A high-valent heterobimetallic catalyst namely [Ir2(COD)2(SnCl3)2(Cl)2(μ-Cl)2] (5 mol %), or dual catalyst system of [Ir(COD)Cl]2 (1 mol %) and SnCl4 (4 mol %), promotes the benzylation or allylation of arenes and heteroarenes using ethers as the alkylating agents. An electrophilic mechanism is proposed from a Hammett correlation.
- Podder, Susmita,Roy, Sujit
-
p. 9146 - 9152
(2008/02/09)
-
- Electroorganic reactions. Part 56: Anodic oxidation of 2-methyl- and 2-benzylnaphthalenes: Factors influencing competing pathways
-
A systematic investigation of the anodic oxidation in nucleophilic media of 2-methyl and 2-benzylnaphthalenes, substituted at the 6-position in the naphthalene nucleus and at the 4-phenyl position of the benzylic side chain, has been carried out to identify factors favouring side-chain substitution. Cyclic voltammetry confirms that 6-substitution has a profound effect on the oxidation potentials of the naphthalene nucleus and 13C chemical shifts indicate polar effects at the benzylic carbon. However, little side-chain anodic oxidation is observed under any conditions tried; the radical-cations of electron-rich substrates preferentially dimerise and a strongly electron-withdrawing substituent at the 6-position (EtOSO2) promotes nuclear substitution. In contrast, oxidation with DDQ in aqueous acetic acid gives efficient side-chain oxidation for electron rich substrates, consistent with hydride transfer, possibly intramolecularly via a charge transfer complex.
- Utley, James H.P,Rozenberg, Gregor G
-
p. 5251 - 5265
(2007/10/03)
-
- AROMATIZATION OF ALIPHATIC COMPOUNDS - V. m-DIALKIYL-BENZENES AND 2-BENZYL-NAPHTALENES
-
Same cyclohexadienols, when heated at 220 deg C with PyHCl, gave, through dehydration and isomerisation, the corresponding benzene derivatives.So 2,6-dibenzyliden-cyclohexanols gave m-dibenzyl-benzenes, 2-benzyliden-1-tetralols gave 2-benzyl-naphtalenes a
- Giannangeli, M.,Baiocchi, L.
-
p. 1381 - 1384
(2007/10/02)
-