Coordinative Chain Transfer Polymerization

Valente, Andreia; Mortreux, André; Visseaux, Marc; Zinck, Philippe

doi:10.1021/cr300289z

Cited by 336 publications

(294 citation statements)

References 126 publications

(259 reference statements)

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“…The ratio n(chains)/n(Ln centers) even reached beyond 1, implying minimal amounts of chain transfer. This can be explained by free AlMe3, which has a low capability of serving as a chain transfer agent [47]. This would also cause the occurrence of dormant species as described by Brintzinger et al [48].…”

Section: Screening Studiesmentioning

confidence: 99%

1,3-Diene Polymerization Mediated by Homoleptic Tetramethylaluminates of the Rare-Earth Metals

et al. 2018

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Section: Screening Studiesmentioning

confidence: 99%

1,3-Diene Polymerization Mediated by Homoleptic Tetramethylaluminates of the Rare-Earth Metals

et al. 2018

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“…functionalizability, and control over initiating groups is required. We herein report the one-step diastereoselective and enantioselective construction of the deoxypropionate motif by coordination chain transfer polymerization using an alkylmetal species as a chain-transfer agent (CTA) (18,19). Our objective is to achieve highly stereoselective propylene oligomerization using this method.…”

Section: Significancementioning

confidence: 99%

One-step catalytic asymmetric synthesis of all- syn deoxypropionate motif from propylene: Total synthesis of (2 R ,4 R ,6 R ,8 R )-2,4,6,8-tetramethyldecanoic acid

Ota

Murayama

Nozaki

2016

Proc. Natl. Acad. Sci. U.S.A.

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In nature, many complex structures are assembled from simple molecules by a series of tailored enzyme-catalyzed reactions. One representative example is the deoxypropionate motif, an alternately methylated alkyl chain containing multiple stereogenic centers, which is biosynthesized by a series of enzymatic reactions from simple building blocks. In organic synthesis, however, the majority of the reported routes require the syntheses of complex building blocks. Furthermore, multistep reactions with individual purifications are required at each elongation. Here we show the construction of the deoxypropionate structure from propylene in a single step to achieve a three-step synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid, a major acid component of a preen-gland wax of the graylag goose. To realize this strategy, we focused on the coordinative chain transfer polymerization and optimized the reaction condition to afford a stereo-controlled oligomer, which is contrastive to the other synthetic strategies developed to date that require 3–6 steps per unit, with unavoidable byproduct generation. Furthermore, multiple oligomers with different number of deoxypropionate units were isolated from one batch, showing application to the construction of library. Our strategy opens the door for facile synthetic routes toward other natural products that share the deoxypropionate motif.

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“…On the other hand, and in line with their above-mentioned collaborative transmetallation action, Ae-alkyls can act in such olefin polymerizations as unique reversible transfer agents, leading to so-called CGP. The involvement of Ae-alkyl reagents (essentially dialkylmagnesium derivatives) in this peculiar type of polymerization, which has enjoyed much popularity and witnessed significant progress over the past 2 decades [1][2][3], has also been demonstrated in the polymerization of styrene and conjugated dienes. Although Ae(Mg)-alkyls do not participate as the active polymerization species in these processes, they have enabled the preparation of unique Ae(Mg)-dipolymeryl compounds, which subsequently proved of great utility in macromolecular engineering.…”

Section: Introductionmentioning

confidence: 99%

Alkaline-Earth Metal Complexes in Homogeneous Polymerization Catalysis

Carpentier

Sarazin

2013

Alkaline-Earth Metal Compounds

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This chapter describes the use of complexes of the alkaline-earth metals (magnesium, calcium, strontium, and barium) in homogeneous polymerization catalysis. The latest developments in the polymerization of monomers containing C=C unsaturations (ethylene, styrene, dienes, acrylates) and in the ring-opening polymerization (ROP) of cyclic esters [lactides (LA), ε-caprolactone, trimethylene carbonate] are covered. The mechanisms of chain growth polymerization of olefins and immortal ROP of cyclic esters, which is of particular relevance to these metals, are presented. In view of the current interest devoted to the organometallic chemistry of the larger alkaline-earth metals, the implementation of well-defined catalyst systems based on calcium, strontium, and barium for the polymerizations of styrene and lactide is highlighted

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Coordinative Chain Transfer Polymerization

Cited by 336 publications

References 126 publications

1,3-Diene Polymerization Mediated by Homoleptic Tetramethylaluminates of the Rare-Earth Metals

1,3-Diene Polymerization Mediated by Homoleptic Tetramethylaluminates of the Rare-Earth Metals

One-step catalytic asymmetric synthesis of all- syn deoxypropionate motif from propylene: Total synthesis of (2 R ,4 R ,6 R ,8 R )-2,4,6,8-tetramethyldecanoic acid

Alkaline-Earth Metal Complexes in Homogeneous Polymerization Catalysis

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