Abstract: When aiming at the direct use of CO2 for the preparation of advanced/value-added materials, the synthesis of CO2/olefin copolymers is very appealing but challenging. The δ-lactone 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVP), synthesized by telomerization of CO2 with 1,3-butadiene, is a promising monomer. However, its chemoselective ring-opening polymerization (ROP) is hampered...[En savoir plus]
Abstract: The aromatic Cope rearrangement is an elusive transformation that has been the subject of a limited number of investigations compared to those seemingly close analogues, namely the Cope and aromatic Claisen rearrangement. Herein we report our investigations inspired by moderate success observed in the course of pioneering works. By careful experimental and theoretical investigations,...[En savoir plus]
Abstract An atom-economic and diazo-free strategy for the construction of novel pseudo anomeric C-1 alkenyl spirocyclopropyl sugars is described. Leveraging the 1,2-migration pathway of propargyl esters under gold(I) catalysis, easily available exo-glycals undergo β-selective alkenylcarbenoid insertion in moderate to excellent yields. Preferential activation of propargyl moieties and concerted...[En savoir plus]
Abstract: Analogous to O-glycosides, C-glycosides are natural products exhibiting various bioactivities. Alkynyl C-glycosides represent important key intermediates toward more complex derivatives; however, a convenient access through a single catalytic and highly stereocontrolled step remains an important and only partially solved challenge. Here, a mechanistically designed gold(I)-catalyzed...[En savoir plus]
Abstract: Herein, we report the first visible-light-induced strategy for the rapid synthesis of densely functionalized α- and γ-phosphorylated β-sulfonyl enamines in a regio- and stereoselective fashion from N-sulfonyl allenamides and H-phosphine oxides. The transformation displays a broad susbtrate, while operating at room temperature under photocatalyst- and additive-free conditions. In this...[En savoir plus]
Abstract : This work details the synthesis and characterization of low-coordinate Zn(II)-based organocations [(NHC)Zn(R)]+ incorporating extremely bulky NHCs [ITr] and [IAd] ([ITr] = ([ITr] = [(HCNCPh3)2C:]; [IAd] = [(HCNAd)2C:], Ad = adamantyl)). Their structural features and particularities are thoroughly assessed as well as their air and water tolerance. Neutral ITr and IAd adducts...[En savoir plus]
Abstract : he present report describes the first use of unprotected and “free” N-heterocyclic carbenes (NHCs), such as IMes, IPr and air-stable Cl-IPr carbenes, as single component initiators for the alternating ring-opening co-polymerization (ROCOP) of cyclic anhydrides (phthalic anhydride, PA; succinic anhydride, SA) and various epoxides to efficiently and selectively access the corresponding...[En savoir plus]