Palladium-catalyzed cross-coupling of alcohols with olefins by positional tuning of a counteranion

被引:4
作者
Kaster, Sven H. M. [1 ]
Zhu, Lei [1 ]
Lyon, William L. [1 ]
Ma, Rulin [1 ]
Ammann, Stephen E. [1 ]
White, M. Christina [1 ]
机构
[1] Univ Illinois, Dept Chem, Roger Adams Lab, Urbana, IL 61801 USA
关键词
ALLYLIC ETHERIFICATION; C-H; ALPHA-ALLYLATION; EFFICIENT METHOD; ACID; BOND; SULFOXIDE; COMPLEXES; DIFFUSION; STRATEGY;
D O I
10.1126/science.ado8027
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Transition metal-catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp(3))-O functionalization step have precluded general methods. Here, we describe computationally guided transition metal-ligand design that positions a hydrogen-bond acceptor anion at the reactive site to promote functionalization. A general cross-coupling of primary, secondary, and tertiary aliphatic alcohols with terminal olefins to furnish >130 ethers is achieved. The mild conditions tolerate functionality that is prone to substitution, elimination, and epimerization and achieve site selectivity in polyol settings. Mechanistic studies support the hypothesis that the ligand's geometry and electronics direct positioning of the phosphate anion at the pi-allyl-palladium terminus, facilitating the phosphate's hydrogen-bond acceptor role toward the alcohol. Ligand-directed counteranion positioning in cationic transition metal catalysis has the potential to be a general strategy for promoting challenging bimolecular reactivity.
引用
收藏
页码:1067 / 1076
页数:10
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