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Trityl Cation-Catalyzed Hosomi-Sakurai Reaction of Allylsilane with β,γ-Unsaturated α-Ketoester to Form γ,γ-Disubstituted α-Ketoesters.

ABSTRACT: (Ph₃C)[BPh(^F)₄]-catalyzed Hosomi-Sakurai allylation of allylsilanes with β,γ-unsaturated α-ketoesters has been developed to give γ,γ-disubstituted α-ketoesters in high yields with excellent chemoselectivity. Preliminary mechanistic studies suggest that trityl cation dominates the catalysis, while the silyl cation plays a minor role.

SUBMITTER: Gan Z

PROVIDER: S-EPMC9331905 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Trityl Cation-Catalyzed Hosomi-Sakurai Reaction of Allylsilane with β,γ-Unsaturated α-Ketoester to Form γ,γ-Disubstituted α-Ketoesters.

Gan Zubao Z Cui Deyun D Zhang Hongyun H Feng Ying Y Huang Liying L Gui Yingying Y Gao Lu L Song Zhenlei Z

Molecules (Basel, Switzerland) 20220724 15

(Ph3C)[BPh(F)4]-catalyzed Hosomi-Sakurai allylation of allylsilanes with β,γ-unsaturated α-ketoesters has been developed to give γ,γ-disubstituted α-ketoesters in high yields with excellent chemoselectivity. Preliminary mechanistic studies suggest that trityl cation dominates the catalysis, while the silyl cation plays a minor role. ...[more]

PMID: 35897907

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Project description:Sustainable chemistry requires application of green processes and often starting materials originate from renewable resources. Biomass-derived monomers based on five-membered γ-butyrolactone ring represent suitable candidates to replace sources of fossil origin. α-Methylene-γ-butyrolactone, β-hydroxy-α-methylene-γ-butyrolactone, and β- and γ-methyl-α-methylene-γ-butyrolactones bearing exocyclic double bond are available directly by isolation from plants or derived from itaconic or levulinic acids available from biomass feedstock. Exocyclic double bond with structural similarity with methacrylates is highly reactive in chain-growth polymerization. Reaction involves the linking of monomer molecules through vinyl double bonds in the presence of initiators typical for radical, anionic, zwitterionic, group-transfer, organocatalytic, and coordination polymerizations. The formed polymers containing pendant ring are characterized by high glass transition temperature (T g > 195°C) and render decent heat, weathering, scratch, and solvent resistance. The monomers can also be hydrolyzed to open the lactone ring and form water-soluble monomers. Subsequent radical copolymerization in the presence of cross-linker can yield to hydrogels with superior degree of swelling and highly tunable characteristics, depending on the external stimuli. The five-membered lactone ring allows copolymerization of these compounds by ring opening polymerization to provide polyesters with preserved methylene functionality. In addition, both the lactone ring and the methylene double bond can be attacked by amines. Polyaddition with di- or multi-amines leads to functional poly(amidoamines) with properties tunable by structure of the amines. In this mini-review, we summarize the synthetic procedures for preparation of polymeric materials with interesting properties, including thermoplastic elastomers, acrylic latexes, stimuli-sensitive superabsorbent hydrogels, functional biocompatible polyesters, and poly(amidoamines).

Dataset Information

Trityl Cation-Catalyzed Hosomi-Sakurai Reaction of Allylsilane with β,γ-Unsaturated α-Ketoester to Form γ,γ-Disubstituted α-Ketoesters.

Publications

Trityl Cation-Catalyzed Hosomi-Sakurai Reaction of Allylsilane with β,γ-Unsaturated α-Ketoester to Form γ,γ-Disubstituted α-Ketoesters.

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