| Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies | |
| Department | 绿色化学研究发展中心 |
Cui XJ(崔新江) ; Shi F(石峰); Man Kin Tes; Dirk Gördes; Kerstin Thurow; Matthias Beller; Deng YQ(邓友全)
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| 2009 | |
| Source Publication | Adv. Synth. Catal.
 |
| ISSN | 1615-4150 |
| Volume | 351Pages:2949-2958 |
| Abstract | The N-alkylation of sulfonamides with alcohols is efficiently performed in the presence of easily available copper catalysts via hydrogen borrowing methodology. Applying a copper acetate/potassium carbonate system the reaction of sulfon-ACHTUNGTRENUNGamides and alcohols gave the corresponding secondary amines in excellent yield. In situ HR-MS analysis indicated that bissulfonylated amines are formed under air atmosphere, which act as self-stabilizing ligands for the catalytic system. UV-visible measurements suggest the interaction between the copper centre and the bissulfonylated amine. Reactions of benzyl alcohol-d7 with p-toluenesulfonamide, Nbenzyl-p-toluenesulfonamide or N-benzylidenetolu-ACHTUNGTRENUNGenesulfonamide revealed that the reaction proceeds via a transfer hydrogenation mechanism and the whole process is micro-reversible. Competitive reactions of benzyl alcohol and benzyl alcohol-d7 with ptoluenesulfonamide revealed a kinetic isotope effect (kH/kD) of 3.287 (0.192) for the dehydrogenation of benzyl alcohol and 0.611 (0.033) for the hydrogenation of the N-benzylidene-p-toluACHTUNGTRENUNGenesulfonamide intermediate, which suggests that dehydrogenation of the alcohol is the rate-determining step. |
| Keyword | Alcohols Alkylation C-n Bond Formation Copper Catalysts Sulfonamides |
| Subject Area | 物理化学 |
| Funding Organization | the Chinese Academy of Sciences;the DFG (SPP 1118 and Leibniz prize) and the BMBF. F. Shi thanks the Alexander-von-Humboldt-Stiftung for a Fellowship |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | 绿色催化课题组 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/2292 |
| Collection | 绿色化学研究发展中心 |
| Corresponding Author | Shi F(石峰); Deng YQ(邓友全) |
| Recommended Citation GB/T 7714 | Cui XJ,Shi F,Man Kin Tes,et al. Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies[J]. Adv. Synth. Catal.,2009,351:2949-2958. |
| APA | 崔新江.,石峰.,Man Kin Tes.,Dirk Gördes.,Kerstin Thurow.,...&邓友全.(2009).Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies.Adv. Synth. Catal.,351,2949-2958. |
| MLA | 崔新江,et al."Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies".Adv. Synth. Catal. 351(2009):2949-2958. |
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| Adv. Synth. Catal. 2（283KB） | 开放获取 | License | View Application Full Text | |||
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