Lewis acid-assisted Ir(iii) reductive elimination enables construction of seven-membered-ring sulfoxides

Yang, Wu; Li, Yingzi; Zhu, Jiefeng; Liu, Wentan; Ke, Jie; He, Chuan

2020-10-07

10.1039/d0sc04180g

Chemical Science   影响因子和分区

2041-6520

2041-6539

Iridium has played an important role in the evolution of C-H activation chemistry over the last half century owing to its high reactivity towards stoichiometric C-H bond cleavage; however, the use of Ir(iii) complexes in catalytic C-H functionalization/C-C bond formation appears to have fallen off significantly. The main problem lies in the reductive elimination step, as iridium has a tendency to form stable and catalytically inactive Ir(iii) species. Herein, with a rationally designed Lewis acid assisted oxidatively induced strategy, the sluggish Ir(iii) reductive elimination is successfully facilitated, enabling the facile C-C bond formation. The X-ray crystal structure of a silver salt adduct of iridacycle and DFT calculations demonstrate that the sulfoxide group acts as a key bridge connecting the Ir(iii) metal centre with the silver Lewis acid, which facilitates the reductive elimination of the Ir(iii) metallacycle. Further identification of oxidants was carried out by performing stoichiometric reactions, which enables the development of catalytic construction of various highly functionalized seven-membered-ring sulfoxides, that are of great interest in medicinal chemistry and materials science.

SCI ; EI ; IC ; CCR

英语

NI论文

第一 ; 通讯

Thousand Talents Program for Young Scholars, Shenzhen Science and Technology Innovation Committee[JCYJ20190809142809370] ; Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000573713500011

ROYAL SOC CHEMISTRY

20204209339822

Silver ; Iridium compounds ; Chemical bonds ; Silver halides ; Activation analysis

Precious Metals:547.1 ; Physical Chemistry:801.4 ; Chemical Products Generally:804 ; Crystal Lattice:933.1.1

Web of Science

Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Dept Chem, Shenzhen Grubbs Inst, Shenzhen 518055, Guangdong, Peoples R China

Yang, Wu,Li, Yingzi,Zhu, Jiefeng,et al. Lewis acid-assisted Ir(iii) reductive elimination enables construction of seven-membered-ring sulfoxides[J]. Chemical Science,2020,11(37):10149-10158.

Yang, Wu,Li, Yingzi,Zhu, Jiefeng,Liu, Wentan,Ke, Jie,&He, Chuan.(2020).Lewis acid-assisted Ir(iii) reductive elimination enables construction of seven-membered-ring sulfoxides.Chemical Science,11(37),10149-10158.

Yang, Wu,et al."Lewis acid-assisted Ir(iii) reductive elimination enables construction of seven-membered-ring sulfoxides".Chemical Science 11.37(2020):10149-10158.