Selective Formylation and Methylation of Amines using Carbon Dioxide and Hydrosilane Catalyzed by Alkali-Metal Carbonates

doi:10.1021/acscatal.6b01856

	Selective Formylation and Methylation of Amines using Carbon Dioxide and Hydrosilane Catalyzed by Alkali-Metal Carbonates
	Fang, Chi 1,2; Lu, Chunlei2,3 ; Liu, Muhua2,3 ; Zhu, Yiling2 ; Fu, Yao 1; Lin, Bo-Lin2,3
	2016-11
发表期刊	ACS CATALYSIS (IF:11.3[JCR-2023],12.6[5-Year])
ISSN	2155-5435
卷号	6 期号:11 页码:7876-7881
发表状态	已发表
DOI	10.1021/acscatal.6b01856
摘要	The formylation and methylation of amines with carbon dioxide and hydrosilanes are emerging yet important types of transformations for CO2. Catalytic methods effective for both reactions with wide substrate scopes are rare because of the difficulty in controlling the selectivity. Herein, we report that simple and readily available inorganic bases-alkali-metal carbonates, especially cesium carbonate-catalyze both the formylation and methylation reactions efficiently under mild conditions. The selectivity can be conveniently controlled by varying the reaction temperature and silane. A "cesium effect" on both reactions was observed by comparing the catalytic activity of various alkali-metal carbonates. Combined experimental and computational studies suggested the following reaction mechanism: (i) activation of Si-H by Cs2CO3, (ii) insertion of CO2 into Si-H, (iii) formylation of amines by silyl formate, and (iv) reduction of formamides to methylamines.
关键词	CO2 hydrosilanes amines Cs2CO3 formylation methylation
收录类别	SCI ; EI
语种	英语
资助项目	National Science Foundation of China[NSFC U1532125]
WOS研究方向	Chemistry
WOS类目	Chemistry, Physical
WOS记录号	WOS:000387306100070
出版者	AMER CHEMICAL SOC
EI入藏号	20182005200377
EI主题词	Alkylation ; Amines ; Carbon dioxide ; Carbonates ; Catalyst activity ; Methylation ; Silicon compounds
EI分类号	Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804
WOS关键词	C-C BONDS ; FORMIC-ACID ; N-FORMYLATION ; HOMOGENEOUS HYDROGENATION ; DIPHOSPHINE COMPLEX ; MOLECULAR-HYDROGEN ; ROOM-TEMPERATURE ; SECONDARY-AMINES ; NITRO-COMPOUNDS ; BUILDING-BLOCK
原始文献类型	Article
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/1653
专题	物质科学与技术学院物质科学与技术学院_PI研究组_林柏霖组物质科学与技术学院_PI研究组_李智组物质科学与技术学院_本科生物质科学与技术学院_博士生
通讯作者	Fu, Yao; Lin, Bo-Lin
作者单位	1.Univ Sci & Technol China, Dept Chem, Hefei 230026, Peoples R China 2.ShanghaiTech Univ, SPST, Shanghai 201210, Peoples R China 3.Chinese Acad Sci, Shanghai Inst Organ Chem, Shanghai 200032, Peoples R China
第一作者单位	物质科学与技术学院
通讯作者单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Fang, Chi,Lu, Chunlei,Liu, Muhua,et al. Selective Formylation and Methylation of Amines using Carbon Dioxide and Hydrosilane Catalyzed by Alkali-Metal Carbonates[J]. ACS CATALYSIS,2016,6(11):7876-7881.
APA	Fang, Chi,Lu, Chunlei,Liu, Muhua,Zhu, Yiling,Fu, Yao,&Lin, Bo-Lin.(2016).Selective Formylation and Methylation of Amines using Carbon Dioxide and Hydrosilane Catalyzed by Alkali-Metal Carbonates.ACS CATALYSIS,6(11),7876-7881.
MLA	Fang, Chi,et al."Selective Formylation and Methylation of Amines using Carbon Dioxide and Hydrosilane Catalyzed by Alkali-Metal Carbonates".ACS CATALYSIS 6.11(2016):7876-7881.