Metathesis Reactions of Carbohydrates: Recent Highlights in Alkyne Metathesis

Abstract

Metathesis processes play a prominent role in the development of useful synthetic transformations because of their mildness and tolerance of functional groups. On the other hand, carbohydrates have gained well‐deserved importance in the study of biological processes. This review summarizes a decade of research in the application of alkyne metathesis (AM) reactions in some of its variants to carbohydrates and carbohydrate‐related compounds.

A Survey of Recent Synthetic Applications of 2,3-Dideoxy-Hex-2-enopyranosides

“…More recently, a one-pot multicomponent approach to 3-branched-2,3-unsaturated hexopyranoses 11 has been devised by Botta and co-workers (Scheme 4c) [35]. The protocol, in which a monosubstituted alkyne, ethyl vinyl ether and ethyl glyoxalate were combined, involved an enyne cross-metathesis (Grubb’s catalyst, 2nd generation) [36] leading a diene intermediate ( A ), followed by an in situ HAD reaction.…”

Olefin Cross-Metathesis in Polymer and Polysaccharide Chemistry: A Review

“…In the past several decades, olefin metathesis (OM) has been vigorously developed into a powerful and convenient synthetic tool in organic and polymer chemistry. − Compared with other transition-metal catalyzed carbon–carbon bond formation reactions, OM enjoys the advantage of using commercially available, well-defined, and easily handled catalysts and has a broad scope with respect to product transformations. ,, Figure shows the most common metathesis transformations among different types of olefin-containing compounds. These include ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis polymerization (ADMET), which are well-known methods for polymer synthesis, − ring-closing metathesis (RCM), − which is widely used in the synthesis of complex small molecules, and cross-metathesis (CM), which until recently had been used primarily in small molecule chemistry and industrial processes …”

“…Several air-stable and functional group-tolerant OM catalysts are commercially available; the most commonly used are listed in Figure 3. These include Grubbs' first generation catalyst (1), Grubbs' second generation catalyst (2), and Hoveyda−Grubbs' second generation catalyst (3). With these active, robust catalysts, the range of metathesis olefinic substrates has been significantly expanded, and application of different OM transformations has been widely explored.…”

O-Glicosídeos 2,3-Insaturados: Aplicações, Rearranjo De Ferrier E Reações

“…Existem na literatura diversos artigos relatando diferentes metodologias para obtenção de O-glicosídeos 2,3-insaturados. [55][56][57][58][59][60][61][62][63][64][65][66] Estas metodologias podem ser resumidas em seis propostas principais: 1) uso de eliminação redutiva de dissulfato vicinal proposta por Fraser-Reid e Boctor; 2) rota de Zamojski e Achmatowicz; 3) Reação de hetero Diels-Alder (HDA) de 1,4-dialcoxi-1,3-dieno e compostos carbonílicos ativados; 4) fechamento de anel; 5) abordagem por grupo Guaragna'se; e 6) Rearranjo de Ferrier (Esquema 1).…”