- A Pd-catalyzed, boron ester-mediated, reductive cross-coupling of two aryl halides to synthesize tricyclic biaryls
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Tricyclic biaryls are important scaffold structures in many natural products and lead compounds in drug discovery. The formation of a biaryl unit is often the key step for the synthesis of tricyclic biaryls. Despite significant progress toward the synthesis of biaryl compounds in recent years, the direct cross-coupling of two different aryl halides is still challenging and robust methods are lacking. Herein we report a direct cross-coupling of two different aryl halides in the presence of a palladium catalyst and boron ester, which provides a new and useful complementary method to synthesize tricyclic biaryls.
- Chen, Zhilong,Wang, Xiaodong
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supporting information
p. 5790 - 5796
(2017/07/22)
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- Collective Synthesis of Phenanthridinone through C-H Activation Involving a Pd-Catalyzed Aryne Multicomponent Reaction
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A palladium-catalyzed multicomponent reaction (MCR) involving aryne, CO, and aniline is established for straightforward assembly of a phenanthridinone scaffold through C-H bond activation. Free combination with multiple kinds of readily available anilines and arynes is facilely achieved for phenanthridinone construction without prefunctionalization. Representative natural products were subsequently synthesized through this MCR strategy highly efficiently. Control experiments and interval NMR tracking revealed the mechanism, particularly the key role of CuF2 in determining the aryne-releasing rate from the precursor in this transformation.
- Feng, Minghao,Tang, Bingqing,Xu, Hong-Xi,Jiang, Xuefeng
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supporting information
p. 4352 - 4355
(2016/11/01)
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- Ligand controlled regiodivergent C1 insertion on arynes for construction of phenanthridinone and acridone alkaloids
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A palladium-catalyzed regiodivergent C1 insertion multicomponent reaction involving aryne, CO, and 2-iodoaniline is established to construct the scaffolds of phenanthridinone and acridone alkaloids. Regioselective control is achieved under the guidance of selective ligands. The phenanthridinones are solely obtained under ligand-free condition. In comparison, application of the electron-abundant bidentate ligand dppm afforded the acridones with high efficiency. The release rate of the aryne from the precursor assists the regioselectivity of insertion as well, which was revealed through interval NMR tracking. A plausible mechanism was suggested based on the control experiments. Representative natural products and two types of natural product analogues were synthesized divergently through this tunable method. Divergent alkaloid synthesis: A multicomponent, regioselective approach for palladium-catalyzed C1 insertion is described. This reaction was applied in the divergent synthesis of phenanthridinone and acridone natural product core scaffolds.
- Feng, Minghao,Tang, Bingqing,Wang, Nengzhong,Xu, Hong-Xi,Jiang, Xuefeng
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supporting information
p. 14960 - 14964
(2016/02/05)
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- Palladium-catalyzed cyclization of benzamides with arynes: Application to the synthesis of phenaglydon and N-methylcrinasiadine
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N-Methyl or methoxy benzamides reacted with benzynes in the presence of Pd(OAc)2, organic acid and K2S2O8 in CH3CN yielding tricyclic phenanthridinone derivatives in good yields. This journal is
- Pimparkar, Sandeep,Jeganmohan, Masilamani
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supporting information
p. 12116 - 12119
(2014/12/11)
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- Expeditious approach to the Amarylidaceae alkaloids, crinasiadine and its analogues, via a palladium-catalyzed intramolecular direct C-H arylation
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A simple and efficient approach to the core skeleton of various Amaryllidaceae alkaloids such as phenanthridones, phenanthridines and 5, 6-dihydrophenanthridines has been achieved. The methodology involves a palladium catalyzed direct biaryl-coupling of 2
- Mishra, Sourabh,De, Subhadip,N Kakde, Badrinath,Dey, Dhananjay,Bisai, Alakesh
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p. 1093 - 1102
(2013/09/12)
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- Dilithium tetrachlorocuprate(II) catalyzed oxidative homocoupling of functionalized grignard reagents
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An efficient procedure is described for the oxidative homocoupling of functionalized Grignard reagents using a catalytic amount of dilithium tetrachlorocuprate(II) (CuLi2Cl4) in the presence of pure oxygen gas. This method is applied successfully to a variety of aryl, heteroaryl, alkyl, alkenyl and alkynyl halides, which are converted into the corresponding homocoupled products in good to excellent yields. Georg Thieme Verlag Stuttgart · New York.
- Hua, Si-Kai,Hu, Qiu-Peng,Ren, Jiangmeng,Zeng, Bu-Bing
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p. 518 - 526
(2013/03/29)
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- Cyclopalladation of N-phenylbenzamides: Synthesis and structure of bimetallic palladium(II)-complexes
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Three bimetallic palladium(II) complexes were generated by cyclopalladation of N-methyl-N-phenylbenzamide derivatives, substrates known to undergo oxidative intramolecular cross-coupling via palladium catalysis. These isolable Pd-complexes were characterized by X-ray crystallography. Stoichiometric and catalytic experiments with [(3-methoxy-N-methyl-N-phenylbenzamide)Pd(μ-TFA)] 2 were investigated, and this palladium complex was found to be an effective precatalyst for oxidative cross-coupling.
- Borduas, Nadine,Lough, Alan J.,Dong, Vy M.
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experimental part
p. 247 - 252
(2011/06/24)
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- Regioselectivity in direct arylation of benzanilide possessing oxygen substituent in the benzoyl part using palladium without phosphine ligand
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The direct arylation of benzanilide (1) possessing ether oxygen(s) in benzoyl part was examined under phosphine ligand-free conditions, which afforded ortho-product (2) and para-product (3) in very similar ratio to presence of P(o-Tol)3 conditi
- Harayama, Takashi,Nagura, Chie,Miyagoe, Taeko,Kawata, Yuko,Abe, Hitoshi,Takeuchi, Yasuo
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p. 2609 - 2616
(2011/04/15)
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- Synthesis of 5(6H)-phenanthridones using Diels-Alder reaction of 3-nitro-2(1H)-quinolones acting as dienophiles
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Diels-Alder reactions of 3-nitro-2(1H)-quinolones with 1,3-butadiene derivatives were carried out to give the phenanthridone derivatives under both atmospheric and high pressure conditions. Furthermore, the reactivity of 3-substituted 2(1H)-quinolones acting as a dienophile with 2,3-dimethyl-1,3- butadiene was examined using molecular orbital (MO) calculation.
- Fujita, Reiko,Yoshisuji, Toshiteru,Wakayanagi, Sota,Wakamatsu, Hideaki,Matsuzaki, Hisao
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p. 204 - 208
(2007/10/03)
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- Effect of oxygen substituents on the regioselectivity of the Pd-assisted biaryl coupling reaction of benzanilides
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This study investigated the effect of oxygen substituents in the benzoyl part of N-(2-iodophenyl)benzamide on the coupling position in its Pd-assisted biaryl coupling reaction. Benzamide with methylenedioxy and acyloxy groups yielded the ortho-product for
- Harayama, Takashi,Kawata, Yuko,Nagura, Chie,Sato, Tomonori,Miyagoe, Taeko,Abe, Hitoshi,Takeuchi, Yasuo
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p. 6091 - 6094
(2007/10/03)
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