Recent Developments in the Meyer‐Schuster Rearrangement

Abstract

Most of this review article has been prepared during Covid 19 pandemy. Therefore, we dedicate it,-first to all persons who unfortunately died from this disease and,-second to all people (medical doctors and many others) who helped their congeners to survive to this pandemy. The Meyer-Schuster rearrangement is an efficient method to prepare α,β-unsatured carbonyl compounds starting from propargylic alcohols and this review presents the remarkable progress made during the last decade in this reaction. New efficient catalytic systems have been discovered and many elegant applications have been reported for this rearrangement. To be noticed in particular are the new and efficient cascade processes affording a wide range of carbo-and heterocyclic molecules. Moreover, brilliant applications of this rearrangement have been described as well, in the total synthesis of complex natural products and their analogues. Finally, the first examples of aza-Meyer-Schuster rearrangements have been recently described as well.

Tandem Macrolactone Synthesis: Total Synthesis of (−)‐Exiguolide by a Macrocyclization/Transannular Pyran Cyclization Strategy

“…Accordingly, we further envisioned that tetrahydropyran-containing macrolactone VI might be synthesizable from propargylic alcohol VII (Figure 1d). More specifically, a Meyer-Schuster rearrangement [11] of VII under AuÀ Mo catalysis [12] would provide IV. A macrocyclic RCM [13] of IV should deliver V, which in turn was anticipated to undergo a transannular oxa-Michael addition [14] to afford VI under Au or Ru catalysis.…”

One-Pot Synthesis of Push–Pull Butadienes from 1,3-Diethyl-2-thiobarbituric Acid and Propargylic Alcohols

“…For the preparation of enals 2a,b, Dumur and co-workers followed a classical synthetic route involving the initial olefination of the respective 4,4′-disubstituted benzophenone, and subsequent Vilsmeier formylation of the resulting 1,1-diarylethylenes (see Scheme 1). It is well known that α,β-unsaturated carbonyl compounds (both enals and enones) can be accessed, in a straightforward and atom-economical manner, through the catalytic Meyer-Schuster rearrangement of propargylic alcohols [12][13][14]. In this context, we developed some years ago an efficient, general and environmentally benign protocol for the Meyer-Schuster conversion of terminal propargylic alcohols into enals employing inexpensive InCl3 as the catalyst, water as solvent, and microwaves (MW) irradiation as the heating source (Scheme 2) [15].…”

“…In this context, we developed some years ago an efficient, general and environmentally benign protocol for the Meyer-Schuster conversion of terminal propargylic alcohols into enals employing inexpensive InCl3 as the catalyst, water as solvent, and microwaves (MW) irradiation as the heating source (Scheme 2) [15]. Additionally, in line with the interest of our group in the design of push-pull molecules [16,17], we demonstrated the utility of this MW-assisted InCl3-catalyzed reaction in the field with the high-yield synthesis of the donor-acceptor butadienes 6a,b, structurally related to 3a,b, by coupling of the corresponding propargylic alcohols 4a,b with indan-1,3-dione 5 [18] As shown in Scheme It is well known that α,β-unsaturated carbonyl compounds (both enals and enones) can be accessed, in a straightforward and atom-economical manner, through the catalytic Meyer-Schuster rearrangement of propargylic alcohols [12][13][14]. In this context, we developed some years ago an efficient, general and environmentally benign protocol for the Meyer-Schuster conversion of terminal propargylic alcohols into enals employing inexpensive InCl 3 as the catalyst, water as solvent, and microwaves (MW) irradiation as the heating source (Scheme 2) [15].…”

“…It is well known that α,β-unsaturated carbonyl compounds (both enals and enones) can be accessed, in a straightforward and atom-economical manner, through the catalytic Meyer-Schuster rearrangement of propargylic alcohols [12][13][14]. In this context, we developed some years ago an efficient, general and environmentally benign protocol for the Meyer-Schuster conversion of terminal propargylic alcohols into enals employing inexpensive InCl3 as the catalyst, water as solvent, and microwaves (MW) irradiation as the heating source (Scheme 2) [15].…”

Meyer-Schuster Rearrangement—Convenient Synthesis of α,β-Unsaturated α-Iodinated Aldehydes and Ketones

“…Several Meyer-Schuster reactions have been described in two recently published review articles. [4,5] Figure 1 Meyer-Schuster rearrangement of propargyl alcohols.…”