Methods for the synthesis of O-, S- and N-vinyl derivatives

Abstract

The currently known methods for the preparation of vinyl ethers, vinyl sulfides and enamines are analyzed and described systematically. The published data on the reactions of alcohols, thiols and various nitrogen-containing compounds with acetylene, resulting in the corresponding vinyl derivatives, are considered. The attention is focused on the application of convenient acetylene sources. Other modern approaches to the synthesis of vinyl derivatives are described in detail, including vinyl exchange and metathesis reactions, various types of cross-coupling and cleavage of organic compounds. Some specific synthetic routes to vinyl ethers, vinyl sulfides and enamines are presented in the last Section. The bibliography includes 262 references.

Towards C1 chemistry: methanol vinylation by CaC2 in water in the presence of potassium or sodium carbonates

“…However, a surprising result was the high catalytic activity of Na 2 CO 3 which allowed a conversion/yield value of 43% with 12.5% loading (Table , entry 15) to be obtained. It is indeed unexpected because sodium‐tailored bases, alkoxides or hydroxides are much inferior catalysts in vinylation of alcohols with acetylene compared with the corresponding potassium‐derived bases . Although under the same conditions the yield of MVE obtained with Na 2 CO 3 is 15% less compared to that with K 2 CO 3 (43 and 58%, correspondingly), the use of the former in real technological processes might be more preferential owing to economic reasons (Na 2 CO 3 is about 3–5 times cheaper than K 2 CO 3 ).…”

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

“…A typical example is the preparation of vinyl thioethers, which are the principal building blocks for the incorporation of sulfur functional groups through polymerization. However, most currently employed protocols for obtaining vinyl derivatives have major drawbacks (low yields/selectivities, hazardous byproducts, or technical complications) . Introducing calcium carbide as an in situ source of acetylene allows high yields of the O‐, S‐, and N‐vinyl derivatives to be obtained in a completely green manner.…”

“…However, most currently employed protocols for obtaining vinyl derivatives have major drawbacks (low yields/selectivities, hazardous byproducts, or technical complications). [22] Introducing calcium carbide as an in situ sourceo fa cetylene allows high yields of the O-, S-, and N-vinyl derivatives to be obtainedi nacompletely green manner.T his approachi sp erfectly applicable to the synthesis of vinyl thioethers [93] (Scheme 16). In situ released acetylene immediately reacts with thiols;i ts continuouse xpenditure throughout the reactionp revents the development of extra pressure inside the reactor.T he procedure can be modified to involve heterocyclic moieties, [94] whereas potentially hazardous thiols can be replaced with disulfides.…”

“…Its transportation is lessr isky,t here is no need to use complicated high-pressure equipment, and working with it is generally safer and more convenient. [21,22] Herein, we emphasize the sustainable potentialo fc alcium carbidef or av arietyo fh ighly valuabled irections. We support this viewpoint with as urvey of literature published from 2015 to 2018.…”

“…CaC 2 has a number of advantages over gaseous acetylene. Its transportation is less risky, there is no need to use complicated high‐pressure equipment, and working with it is generally safer and more convenient …”