Co-Catalyzed Metal-Ligand Cooperative Approach for N-alkylation of Amines and Synthesis of Quinolines via Dehydrogenative Alcohol Functionalization

Herein we report a cobalt-catalyzed sustainable approach for C-N cross-coupling reaction between amines and alcohols. Using a well-defined Co-catalyst 1 a bearing 2-(phenyldiazenyl)-1,10-phenanthroline ligand, various N-alkylated amines were synthesized in good yields. 1 a efficiently alkylates diamines producing N, N & PRIME;-dialkylated amines in good yields and showed excellent chemoselectivity when oleyl alcohol and & beta;-citronellol, containing internal carbon-carbon double bond were used as alkylating agents. 1 a is equally compatible with synthesizing N-heterocycles via dehydrogenative coupling of amines and alcohols. 1H-Indole was synthesized via an intramolecular dehydrogenative N-alkylation reaction, and various substituted quinolines were synthesized by coupling of 2-aminobenzyl alcohol and secondary alcohols. A few control reactions and spectroscopic experiments were conducted to illuminate the plausible reaction mechanism, indicating that the 1 a-catalyzed N-alkylation proceeds through the borrowing hydrogen pathway. The coordinated arylazo ligand participates actively throughout the reaction; the hydrogen eliminated during dehydrogenation of alcohols was set aside in the ligand backbone and subsequently gets transferred in the reductive amination step to imine intermediates yielding N-alkylated amines. On the other hand, 1 a-catalyzed quinoline synthesis proceeds through dehydrogenation followed by successive C-C and C-N coupling steps forming H2O2 as a by-product under air.

Automated summary

Herein, a cobalt-catalyzed sustainable approach for C-N cross-coupling reaction between amines and alcohols is reported. The well-defined Co-catalyst 1 a with a 2-(phenyldiazenyl)-1,10-phenanthroline ligand efficiently alkylates diamines producing N,N'-dialkylated amines and shows excellent chemoselectivity. This catalyst is also compatible with synthesizing N-heterocycles via dehydrogenative coupling of amines and alcohols.