Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies

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	Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies
	Deng YQ(邓友全); Deng YQ(邓友全); Shi F(石峰); Cui XJ(崔新江)
刊名	Adv. Synth. Catal.
	2009
卷号	351 页码:2949-2958
关键词	alcohols alkylation C-N bond formation copper catalysts sulfonamides
ISSN号	1615-4150
通讯作者	石峰 ; 邓友全
中文摘要	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.
学科主题	物理化学
收录类别	SCI
资助信息	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
语种	英语
WOS记录号	WOS:000272392000026
公开日期	2012-12-01
内容类型	期刊论文
源URL	[http://210.77.64.217/handle/362003/2292]
专题	兰州化学物理研究所_绿色化学研究发展中心
通讯作者	Deng YQ(邓友全); Deng YQ(邓友全); Shi F(石峰)
推荐引用方式 GB/T 7714	Deng YQ,Deng YQ,Shi F,et al. Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies[J]. Adv. Synth. Catal.,2009,351:2949-2958.
APA	邓友全,邓友全,石峰,&崔新江.(2009).Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies.Adv. Synth. Catal.,351,2949-2958.
MLA	邓友全,et al."Copper-Catalyzed N-Alkylation of Sulfonamides with Benzylic Alcohols: Catalysis and Mechanistic Studies".Adv. Synth. Catal. 351(2009):2949-2958.