Eight-membered-ring diaminocarbenes bearing naphthalene moiety in the backbone: DFT studies, synthesis of amidinium salts, generation of free carbene, metal complexes, and solvent-free copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction

Gleb A Chesnokov; Maxim A Topchiy; Pavel B Dzhevakov; Pavel S Gribanov; Aleksandr A Tukov; Victor N Khrustalev; Andrey F Asachenko; Mikhail S Nechaev

doi:10.1039/c6dt04484k

Eight-membered-ring diaminocarbenes bearing naphthalene moiety in the backbone: DFT studies, synthesis of amidinium salts, generation of free carbene, metal complexes, and solvent-free copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction

Dalton Trans. 2017 Mar 27;46(13):4331-4345. doi: 10.1039/c6dt04484k.

Authors

Gleb A Chesnokov¹, Maxim A Topchiy², Pavel B Dzhevakov³, Pavel S Gribanov⁴, Aleksandr A Tukov⁴, Victor N Khrustalev⁵, Andrey F Asachenko⁴, Mikhail S Nechaev³

Affiliations

¹ M. V. Lomonosov Moscow State University, Leninskie Gory 1 (3), Moscow, 119991, Russia. Mikhail S. Nechaev m.nechaev@ips.ac.ru m.s.nechaev@org.chem.msu.ru.
² A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky Prospect 29, Moscow, 119991, Russia and A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow, 119991, Russia.
³ M. V. Lomonosov Moscow State University, Leninskie Gory 1 (3), Moscow, 119991, Russia. Mikhail S. Nechaev m.nechaev@ips.ac.ru m.s.nechaev@org.chem.msu.ru and A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky Prospect 29, Moscow, 119991, Russia.
⁴ A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky Prospect 29, Moscow, 119991, Russia.
⁵ A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow, 119991, Russia and Department of Inorganic Chemistry, Peoples' Friendship University of Russia, Miklukho-Maklay Street 6, Moscow, 117198, Russia.

PMID: 28281713
DOI: 10.1039/c6dt04484k

Abstract

A new type of eight-membered ring N-heterocyclic carbene (NHC) bearing a rigid naphthalene moiety in the backbone is reported for the first time. Stereoelectronic properties of 4,5-dihydro-1H-naphtho[1,8-ef][1,3]diazocin-3(2H)-ylidene (NaphtDHD) and smaller ring NHCs were theoretically studied at the DFT level. Amidinium salts were prepared from corresponding amidines and dibromides. Free carbene NaphtDHD-Dipp (Dipp = 2,6-diisopropylphenyl) was generated in solution by treatment of the corresponding salt with LiHMDS. It is stable in solution at low temperatures, while decomposing rapidly at room temperature. Silver(i) and copper(i) complexes were synthesized and structurally characterized in the solid state. The copper(i) complex [(NaphtDHD-Mes)CuBr] (Mes = mesityl, 2,4,6-trimethylphenyl) exhibits high catalytic activity in alkyne-azide cycloaddition (CuAAC) reaction under solvent-free conditions.