Synthesis of 2-Alkoxyaryl-2-aryl Enamines via Tandem Copper-Catalyzed Cycloaddition and Rhodium-Catalyzed Alkoxyarylation from Alkynes, N-Sulfonyl Azides, and Aryl Ethers

Abstract

A synthetic route to a wide range of 2-alkoxyaryl-2-aryl enamines is developed from Rh-catalyzed alkoxyarylation of N-sulfonyl-4-aryl-1,2,3-triazoles with aryl ethers via the elimination of nitrogen molecule. In addition, 2-alkoxyaryl-2-aryl enamines are prepared via tandem Cu-catalyzed cycloaddition and Rh-catalyzed alkoxyarylation starting from alkynes, N-sulfonyl azides, and aryl ethers in one-pot.

Stereoselective Synthesis of (Z)‐β‐Enamido Triflates and Fluorosulfonates from N‐Fluoroalkylated Triazoles

“…N ‐Sulfonyl triazoles, precursors of azavinyl carbenes, are known to undergo a variety of rhodium‐catalyzed reactions. They have been used for the preparation of different types of heterocycles, N ‐sulfonyl‐containing compounds, and for stereoselective synthesis of 2,2‐diaryl or 2‐alkyl‐2‐aryl‐ substituted N ‐sulfonyl enamides (Figure B) . We have recently shown that N ‐fluoroalkyl triazoles prepared by a [3+2] cycloaddition of stable and safe azido(per)fluoroalkanes and alkynes are efficiently transformed to new N ‐fluoroalkyl heterocycles via rhodium carbenoids .…”

“…They have been used for the preparation of different types of heterocycles, N-sulfonyl-containing compounds, [27] and for stereoselectives ynthesiso f2 ,2-diaryl or 2-alkyl-2-aryl-substituted N-sulfonyl enamides ( Figure 1B). [28][29][30][31][32][33] We have recently shown that N-fluoroalkyl triazoles prepared by a[ 3 + +2] cycloaddition of stable and safe azido(per)fluoroalkanes anda lkynes [34][35][36] are efficiently transformed to new N-fluoroalkyl heterocycles via rhodiumc arbenoids. [37,38] However,t he reactivity profiles of Nfluoroalkyl triazoles and N-sulfonyl triazoles are markedlyd ifferent.…”

Tandem 1,2-sulfur migration and (aza)-Diels–Alder reaction of β-thio-α-diazoimines: rhodium catalyzed synthesis of (fused)-polyhydropyridines, and cyclohexenes

“…In the past few years, the use of readily accessible N -sulfonyl-1,2,3-triazoles 4 as a source of α-diazoimines has been greatly exploited in organic synthesis as a vital reactive intermediate. 5 Unlike traditional α-oxo metal carbenoids, metal carbenoids generated from α-diazoimines possess both an electrophilic carbon atom and nucleophilic nitrogen atom, which allows interesting inter/intramolecular reactions with various functional groups, like nitriles, 6 alkynes, 7 alkenes, 8 enol ethers 9 /enamines, 10 carbonyl compounds, 11 cumulenes, 12 C–H, 13 X–H 14 and C–X 15 bonds and other carbene induced transformations to functionalized carbo(hetero)cycles 16 and heteroatom-based building blocks. 17 Interestingly, 1,2-hydride or alkyl migrations onto the electrophilic carbenoid carbon of α-imino metalcarbenes were also reported.…”

Selective Functionalization of Aromatic C(sp2)−H Bonds in the Presence of Benzylic C(sp3)−H Bonds by Electron‐Deficient Carbenoids Generated from 4‐Acyl‐1‐Sulfonyl‐1,2,3‐Triazoles

“…It was reported that 4‐phenyltriazole reacted with anisole ( 5 c ) and N , N ‐diethylaniline ( 5 d ) at 100 °C to afford the corresponding insertion products resulting from reactions at the para C(sp 2 )−H bonds. 4 a also gave the para ‐substituted products 9 and 10 when 5.0 equivalents of 5 c and 5 d , respectively, was used in 0.5 mL of chloroform at lower temperatures (conditions B) [Eqs.…”