Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

被引：5

作者：

Vummaleti, Sai Vikrama Chaitanya ^{[1
]}

Al-Ghamdi, Miasser ^{[1
,4
]}

Poater, Albert ^{[2
,3
]}

Falivene, Laura ^{[1
]}

Scaranto, Jessica ^{[4
]}

Beetstra, Dirk J. ^{[4
]}

Morton, Jason G. ^{[4
]}

Cavallo, Luigi ^{[1
]}

机构：

[1] King Abdullah Univ Sci & Technol, Phys Sci & Engn Div, KAUST Catalysis Ctr, Thuwal 239556900, Saudi Arabia

[2] Univ Girona, Inst Quim Computac & Catalisi, Girona 17071, Catalonia, Spain

[3] Univ Girona, Dept Quim, Girona 17071, Catalonia, Spain

[4] SABIC CRI, Fundamental Catalysis, Thuwal 239556900, Saudi Arabia

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 23期

关键词：

GAUSSIAN-BASIS SETS; OXIDATIVE OXYARYLATION; CIS-DIHYDROXYLATION; OLEFIN INSERTION; INTERNAL ALKENES; BOND ACTIVATION; ATOMS LI; O BOND; OXYGEN; TETRAHYDROFURANS;

D O I：

10.1021/acs.organomet.5b00749

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [Rh-I(dppp)(+)] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pcd/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center.

引用

页码：5549 / 5554

页数：6