- Transition-Metal-Catalyzed Transformation of Sulfonates via S-O Bond Cleavage: Synthesis of Alkyl Aryl Ether and Diaryl Ether
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The catalytic conversion of sulfonates, a versatile class of pharmaceutical intermediates, is usually based on C-O bond cleavage. In this paper, however, we discover a rare transformation of sulfonates via S-O bond cleavage catalyzed by transition metal, through which alkyl sulfonates could undergo an intramolecular desulfitative C-O coupling to form aryl alkyl ethers in the presence of a nickel catalyst. Meanwhile, aryl sulfonates perform similarly to give diaryl ethers catalyzed by a palladium complex. This transformation could tolerate a wide range of functionalities. Controlled experiments reveal that the 2-pyridyl group is necessary to promote the reaction as designed. Crossover experiments proved that this transformation might proceed partly in an intermolecular pathway.
- Chen, Xuemeng,Xiao, Xue,Sun, Haotian,Li, Yue,Cao, Haolin,Zhang, Xuemei,Yang, Shengyong,Lian, Zhong
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supporting information
p. 8879 - 8883
(2019/11/14)
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- Substituent Effects of 2-Pyridones on Selective O-Arylation with Diaryliodonium Salts: Synthesis of 2-Aryloxypyridines under Transition-Metal-Free Conditions
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An efficient transition-metal-free strategy to synthesize 2-aryloxypyridine derivatives has been developed by a selective O-arylation of 2-pyridones with diaryliodonium salts. The reaction was compatible with a series of functional groups for 2-pyridones and diaryliodonium salts such as halides, nitro, cyano, and ester groups. The substituents at the C6-position of 2-pyridones favored O-arylation products because of steric hindrance. The reaction was easily performed on a gram-scale and 6-chloro-2-pyridone was a good precursor to access various unsubstituted 2-aryloxypyridines by dehalogenation. A P2Y 1 lead compound analogue could be prepared in good yield over two steps.
- Li, Xiao-Hua,Ye, Ai-Hui,Liang, Cui,Mo, Dong-Liang
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p. 1699 - 1710
(2018/02/06)
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- Synthesis of m-Alkylphenols via a Ruthenium-Catalyzed C-H Bond Functionalization of Phenol Derivatives
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The first example of the synthesis of m-alkylphenols via a ruthenium-catalyzed CAr-H bond functionalization of phenol derivatives with sec/tert-alkyl bromides is reported. Mechanistic studies indicated that the m-CAr-H bond alkylation may involve a radical process and that a six-membered ruthenacycle complex was the active catalyst. Moreover, this approach can provide an expedited strategy for the atom-/step-economical synthesis of many noteworthy pharmaceuticals and other functional molecules.
- Li, Gang,Gao, Panpan,Lv, Xulu,Qu, Chen,Yan, Qingkai,Wang, Ya,Yang, Suling,Wang, Junjie
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supporting information
p. 2682 - 2685
(2017/05/24)
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- A copper-based metal-organic framework as an efficient and reusable heterogeneous catalyst for ullmann and goldberg type C-N coupling reactions
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A highly porous metal-organic framework (Cu-TDPAT), constructed from a paddle-wheel type dinuclear copper cluster and 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT), has been tested in Ullmann and Goldberg type C-N coupling reactions of a wide range of primary and secondary amines with halobenzenes, affording the corresponding N-arylation compounds in moderate to excellent yields. The Cu-TDPAT catalyst could be easily separated from the reaction mixtures by simple filtration, and could be reused at least five times without any significant degradation in catalytic activity.
- Long, Wei,Qiu, Wenge,Guo, Chongwei,Li, Chuanqiang,Song, Liyun,Bai, Guangmei,Zhang, Guizhen,He, Hong,Kuznetsov, Maxim L.
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p. 21178 - 21192
(2016/01/25)
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- Cycloauration of substituted 2-phenoxypyridine derivatives and X-ray crystal structure of gold, dichloro[2-[[5-[(cyclopentylamino) carbonyl]-2-pyridinyl-κN]oxy]phenyl-κC]-, (SP-4-3)-
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Direct cycloauration of 2-phenoxypyridines with different substituents at the 5-position of the pyridine ring was carried out in an CH3CN/H2O medium, leading to isolation of cycloaurated compounds AuCl2(L) (HL = substitute
- Zhu, Yongbao,Cameron, Beth R.,Skerlj, Renato T.
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- The Structure-Reactivity-Chemoselectivity Relationship on the Reactions of 1-Unsubstituted Tautomeric 2-Pyridones with Benzyne
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The reactions of 2-pyridones with benzyne were investigated in order to gain some insight into the structure-reactivity-chemoselectivity relatinoship involved in the tautomeric systems.All reactions examined have resulted in the formation of Diels-Alder and Michael-type adducts.It has been shown that the Diels-Alder reactivities were well correlated with the HOMO energy levels of the 2-pyridone form and the yields of the Michael-type adduct were closely associated with the tautomeric equilibria.In summary, the chemoselectivities of 2-pyridones in the reaction with benzyne were largely affected by the tautomeric properties.
- Kuzuya, Masayuki,Noguchi, Akihiro,Mano, Ei-ichi,Okuda, Takachiyo
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p. 1149 - 1155
(2007/10/02)
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