Ruthenium-catalyzed ortho-selective C-H alkenylation of aromatic compounds with alkenyl esters and ethers

Yohei Ogiwara, Masaru Tamura, Takuya Kochi, Yusuke Matsuura, Naoto Chatani, Fumitoshi Kakiuchi

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

A direct, regioselective alkenylation of aromatic C-H bonds of aryl- and heteroarylpyridines and related compounds with alkenyl esters was developed using Ru(cod)(cot) as a catalyst. Aromatic compounds bearing electronically diverse substituents and various heterocyclic directing groups are reacted with alkenyl acetates bearing mono- and disubstituted alkenyl groups with aliphatic and aromatic substituents to give ortho-alkenylation products in high yields. The results of deuterium-labeling experiments and competition reactions using different ratios of the E and Z isomers of β-styryl acetate suggested that the C-H alkenylation proceeded via a ruthenium-alkene intermediate and the C-O bond of the alkenyl acetate was cleaved by β-acetoxy elimination. Two types of catalytically relevant species were identified, and the reactivities of these species, combined with the results of the kinetic studies, suggest that the rate-limiting step is the exchange of the COD ligand with the alkenyl ester. On the basis of the elucidated mechanism, the first catalytic coupling reaction using aromatic C-H bonds with C-O bonds of ethers was also developed.

Original languageEnglish
Pages (from-to)402-420
Number of pages19
JournalOrganometallics
Volume33
Issue number1
DOIs
Publication statusPublished - 2014 Jan 13

Fingerprint

Alkenylation
Ethers
Ruthenium
aromatic compounds
Aromatic compounds
Bearings (structural)
ruthenium
esters
acetates
ethers
Esters
Acetates
crack opening displacement
Deuterium
Alkenes
Isomers
Labeling
alkenes
marking
deuterium

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Ruthenium-catalyzed ortho-selective C-H alkenylation of aromatic compounds with alkenyl esters and ethers. / Ogiwara, Yohei; Tamura, Masaru; Kochi, Takuya; Matsuura, Yusuke; Chatani, Naoto; Kakiuchi, Fumitoshi.

In: Organometallics, Vol. 33, No. 1, 13.01.2014, p. 402-420.

Research output: Contribution to journalArticle

Ogiwara, Yohei ; Tamura, Masaru ; Kochi, Takuya ; Matsuura, Yusuke ; Chatani, Naoto ; Kakiuchi, Fumitoshi. / Ruthenium-catalyzed ortho-selective C-H alkenylation of aromatic compounds with alkenyl esters and ethers. In: Organometallics. 2014 ; Vol. 33, No. 1. pp. 402-420.
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