A Reaction of Triazoles with Thioesters to Produce β‐Sulfanyl Enamides by Insertion of an Enamine Moiety into the Sulfur–Carbonyl Bond

154

While thioesters are common intermediates in biochemical processes, they are much less appreciated in organic synthesis, also compared to other carboxylic acid derivatives. However, their chemistry and reactivity is intriguing and diversified, reaching much further than the acyl substitution and aldol chemistry. Herein, we focus on metal-catalyzed reactions for the synthesis of thioesters as well as their transformations. Reactions such as thiocarbonylation, cross-coupling, decarbonylation, allylic substitution or dual photoredox/metal catalysis are discussed. On one hand, new atom economic methods allow for convenient synthesis of thioesters from well available starting materials. On the other hand, various synthetically important compounds can by synthesized due to the multifaceted reactivity of thioesters that we aimed to depict.

Section: In C(o)àsbond Cleavage and Transfer Reactionsmentioning

confidence: 99%

“…Reactionoft hioesterswith triazines catalyzedbyaR h II dimer. [100] Scheme33. Rh-catalyzed acyl transferr eaction of thioestersa nd ketones.…”

Section: In Photoredox Catalysismentioning

confidence: 99%

Metal‐Catalyzed Synthesis and Use of Thioesters: Recent Developments

Hirschbeck

Gehrtz

Fleischer

2018

154

“…Murakami, Miura, and co‐workers reported the rhodium‐catalyzed reaction of N ‐sulfonyl‐1,2,3‐triazoles 1 with thioesters 194 to give β‐sulfanyl enamides (Scheme ) . Compared to the benzamides, the sulfur atom is more nucleophilic than the carbonyl oxygen atom.…”

Section: Reactions Of N‐sulfonyl‐123‐triazolesmentioning

confidence: 99%

Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α‐Imino Rhodium Carbene Complexes Derived from N‐Sulfonyl‐1,2,3‐triazoles

Jiang

Sun

Tang

et al. 2016

212

In recent years, α-imino rhodium carbene complexes derived by ring-opening of N-sulfonyl-1,2,3-triazoles have attracted much attention from organic chemists. Many transformations of these species have been reported that involve, in most cases, nucleophilic attack at the carbene center of the α-imino rhodium carbene, facilitating the synthesis of a wide range of novel and useful compounds, particularly heterocycles. This Minireview mainly focuses on advances in the transformation of N-sulfonyl-1,2,3-triazoles during the past two years.

“…[8] Based on the dipole feature of the in situ generated a-iminocarbene, an array of [3+ +2] cycloaddition reactions have been developed by employingu nsaturated compounds including alkynes, [9] alkenes, [10] allenes, [11] isocyanides, [12] nitriles, [13] aldehydes, [14] furans, [15] and indoles [16] as the reaction counterparts to deliver the nitrogen-containingh eterocycles. [17] More recently,t he groups of Tang, Lee, Anbarasan, Li, and Murakami have reported that enol ethers (Scheme 1a)a nd 2-(siloxy)furans (Scheme 1b)c ouldr eact with 1-sulfonyl-1,2,3-triazoles in the presence of rhodiumcatalysis to give pyrrole, lactam, and dihydropyridine derivatives. [15,18] Tang and co-workers have also described an efficient synthesis of 2,5-dihydroazepinest hrough formal aza-[3+ +2] cycloadditions of triazoles with 1,3-dienes (Scheme 1c).…”

Section: Introductionmentioning

confidence: 99%

Rhodium‐Catalyzed Denitrogenative [3+2] Cycloaddition: Access to Functionalized Hydroindolones and the Framework of Montanine‐Type Amaryllidaceae Alkaloids

Yang

Hou

Cheng

et al. 2017

Rhodium-catalyzed denitrogenative [3+2] cycloaddition of 1-sulfonyl-1,2,3-triazoles with cyclic silyl dienol ethers has been developed for the synthesis of functionalized hydroindolones or their corresponding silyl ethers. The present method has been employed to construct synthetically valuable bicyclo[3.3.1]alkenone derivatives and pyrrolidine-ring-containing bicyclic indole compounds. As a further synthetic application, a stereoselective synthesis of 5,11-methanomorphanthridin-3-one, which shares a key skeleton with montanine-type Amaryllidaceae alkaloids has been achieved by using this chemistry.