Hoveyda-Grubbs catalysts with an N→Ru coordinate bond in a six-membered ring. Synthesis of stable, industrially scalable, highly efficient ruthenium metathesis catalysts and 2-vinylbenzylamine ligands as their precursors

Kirill B Polyanskii; Kseniia A Alekseeva; Pavel V Raspertov; Pavel A Kumandin; Eugeniya V Nikitina; Atash V Gurbanov; Fedor Ivanovich Zubkov

doi:10.3762/bjoc.15.73

Hoveyda-Grubbs catalysts with an N→Ru coordinate bond in a six-membered ring. Synthesis of stable, industrially scalable, highly efficient ruthenium metathesis catalysts and 2-vinylbenzylamine ligands as their precursors

Beilstein J Org Chem. 2019 Mar 22:15:769-779. doi: 10.3762/bjoc.15.73. eCollection 2019.

Authors

Kirill B Polyanskii¹, Kseniia A Alekseeva¹, Pavel V Raspertov¹, Pavel A Kumandin¹, Eugeniya V Nikitina¹, Atash V Gurbanov^{2

3}, Fedor Ivanovich Zubkov¹

Affiliations

¹ Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow 117198, Russian Federation.
² Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
³ Organic Chemistry Department, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan.

Abstract

A novel and efficient approach to the synthesis of 2-vinylbenzylamines is reported. This involves obtaining 2-vinylbenzylamine ligands from tetrahydroisoquinoline by alkylation and reduction followed by the Hofmann cleavage. The resultant 2-vinylbenzylamines allowed us to obtain new Hoveyda-Grubbs catalysts, which were thoroughly characterised by NMR, ESIMS, and X-ray crystallography. The utility of this chemistry is further demonstrated by the tests of the novel catalysts (up to 10^-2 mol %) in different metathesis reactions such as cross metathesis (CM), ring-closing metathesis (RCM) and ring-opening cross metathesis (ROCM).

Keywords: 2-vinylbenzylamine; CM; Hoveyda–Grubbs catalyst; RCM; ROCM; cross metathesis; olefin metathesis; ring-closing metathesis; ring-opening cross metathesis; ruthenium metathesis catalyst; styrene.