Iridium(I)-Catalyzed Intramolecular Cycloisomerization of Enynes: Scope and Mechanistic Course

被引：24

作者：

Fernandez, David F. ^{[1
]}

Rodrigues, Catarina A. B. ^{[1
]}

Calvelo, Martin ^{[1
]}

Gulias, Moises ^{[1
]}

Mascarenas, Jose L. ^{[1
]}

Lopez, Fernando ^{[1
,2
]}

机构：

[1] Univ Santiago Compostela, Dept Quim Organ, Ctr Singular Invest Quim Biol & Mat Mol CiQUS, Santiago De Compostela 15782, Spain

[2] CSIC, Inst Quim Organ Gen, Juan Cierva 3, E-28006 Madrid, Spain

来源：

ACS CATALYSIS | 2018年 / 8卷 / 08期

基金：

欧洲研究理事会;

关键词：

iridium; C-H activation; hydrocarbonation; catalysis; cyclization; IRIDIUM-CATALYZED HYDROARYLATION; H BOND ACTIVATION; C-H; VINYL ETHERS; ALKYLATION; ALKENES; ALKYNES; ORIGINS; ALKENYLATION; SELECTIVITY;

D O I：

10.1021/acscatal.8b02139

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We report an Ir(I)-catalyzed cycloisomerization methodology that provides access to carbocyclic systems bearing exo-alkene moieties from alkynyl-equipped acyclic precursors. The method relies on the C-H activation of olefinic and (hetero)aromatic C(sp(2))-H bonds, followed by an exocyclization to a tethered alkyne, and provides interesting cyclic diene products that are amenable of further elaboration. Importantly, DFT calculations suggests that, in contrast to related hydrocarbonations of alkenes in which either migratory insertions or C-C reductive eliminations have been suggested to be rate-determining, in our reactions, the energetic barrier of these steps is lower than that of the previous C-H activation.

引用

页码：7397 / 7402

页数：11

共 45 条

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