Controlled Selectivity through Reversible Inhibition of the Catalyst: Stereodivergent Semihydrogenation of Alkynes

化学 烯烃 催化作用 异构化 炔烃 组合化学 选择性 硫醇 光化学 有机化学
作者
Jie Luo,Yaoyu Liang,Michael Montag,Yael Diskin‐Posner,Liat Avram,David Milstein
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:144 (29): 13266-13275 被引量:13
标识
DOI:10.1021/jacs.2c04233
摘要

Catalytic semihydrogenation of internal alkynes using H2 is an attractive atom-economical route to various alkenes, and its stereocontrol has received widespread attention, both in homogeneous and heterogeneous catalyses. Herein, a novel strategy is introduced, whereby a poisoning catalytic thiol is employed as a reversible inhibitor of a ruthenium catalyst, resulting in a controllable H2-based semihydrogenation of internal alkynes. Both (E)- and (Z)-alkenes were obtained efficiently and highly selectively, under very mild conditions, using a single homogeneous acridine-based ruthenium pincer catalyst. Mechanistic studies indicate that the (Z)-alkene is the reaction intermediate leading to the (E)-alkene and that the addition of a catalytic amount of bidentate thiol impedes the Z/E isomerization step by forming stable ruthenium thiol(ate) complexes, while still allowing the main hydrogenation reaction to proceed. Thus, the absence or presence of catalytic thiol controls the stereoselectivity of this alkyne semihydrogenation, affording either the (E)-isomer as the final product or halting the reaction at the (Z)-intermediate. The developed system, which is also applied to the controllable isomerization of a terminal alkene, demonstrates how metal catalysis with switchable selectivity can be achieved by reversible inhibition of the catalyst with a simple auxiliary additive.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
大幅提高文件上传限制,最高150M (2024-4-1)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
郎治宇发布了新的文献求助10
刚刚
白云完成签到,获得积分10
刚刚
kimiweiwei完成签到,获得积分10
1秒前
何三岁完成签到,获得积分10
1秒前
朴素幻柏完成签到,获得积分10
2秒前
Hello应助照烧鸡腿采纳,获得10
3秒前
SciGPT应助临水思长采纳,获得10
3秒前
4秒前
4秒前
雪儿完成签到,获得积分10
4秒前
5秒前
有只小狗完成签到,获得积分10
5秒前
共享精神应助子暮采纳,获得10
5秒前
6秒前
ice.sweet完成签到,获得积分10
7秒前
彭于晏应助yy家的小哥哥采纳,获得10
7秒前
7秒前
8秒前
丘比特应助橙子采纳,获得10
8秒前
马路完成签到 ,获得积分10
8秒前
bkagyin应助彩色的芷容采纳,获得10
8秒前
9秒前
清脆代桃发布了新的文献求助10
10秒前
小马甲应助gk采纳,获得10
10秒前
10秒前
11秒前
合适成风完成签到,获得积分10
11秒前
小鸡炖蘑菇完成签到 ,获得积分10
12秒前
12秒前
Orange应助Dreamalive12138采纳,获得10
13秒前
13秒前
lijingwen发布了新的文献求助10
14秒前
善学以致用应助zhao采纳,获得10
14秒前
科研小废物完成签到,获得积分10
14秒前
15秒前
充电宝应助纯洁之心采纳,获得10
15秒前
15秒前
酷波er应助我爱学习采纳,获得10
16秒前
YDM完成签到,获得积分10
16秒前
16秒前
高分求助中
Evolution 10000
ISSN 2159-8274 EISSN 2159-8290 1000
Becoming: An Introduction to Jung's Concept of Individuation 600
Ore genesis in the Zambian Copperbelt with particular reference to the northern sector of the Chambishi basin 500
A new species of Coccus (Homoptera: Coccoidea) from Malawi 500
A new species of Velataspis (Hemiptera Coccoidea Diaspididae) from tea in Assam 500
PraxisRatgeber: Mantiden: Faszinierende Lauerjäger 500
热门求助领域 (近24小时)
化学 医学 生物 材料科学 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 基因 遗传学 催化作用 物理化学 免疫学 量子力学 细胞生物学
热门帖子
关注 科研通微信公众号,转发送积分 3160303
求助须知:如何正确求助?哪些是违规求助? 2811427
关于积分的说明 7892391
捐赠科研通 2470463
什么是DOI,文献DOI怎么找? 1315585
科研通“疑难数据库(出版商)”最低求助积分说明 630884
版权声明 602038