Transition-metal-catalyzed coordination–insertion polymerization of olefins is an indispensable tool in polymer synthesis When polar monomers with polar functional groups are employed, however, the catalysts are often deactivated owing to side reactions such as σ-coordination and β-elimination of the functional group Nevertheless, recent progress in late transition metal catalysis has enabled the synthesis of many types of functional polymers from polar monomers through coordination–insertion polymerization methods This account describes our achievements in the palladium-catalyzed coordination–insertion (co)polymerization of polar monomers for the syntheses of a variety of functional polymers, ranging from functionalized polyolefins via olefin/polar monomer copolymerization to o-arylene-containing polymers via formal aryne polymerization

Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

Although various functionalized units can be incorporated into polyolefins by transition metal catalyzed coordination copolymerizations of nonfunctionalized olefins with polar functional monomers, the incorporated functional units are largely limited to a C1 unit from either CO or C2 units from vinyl monomers. Reported here is the Pd-catalyzed copolymerization of ethylene with cyclopropenone, leading to incorporation of C3 units with functional groups, α,β-unsaturated ketones, in the chain. Coordination-insertion of the carbonyl group and ring opening of the strained three-membered ring are proposed as the key steps in the mechanism. Under different reaction conditions an isolated ketone structure was afforded as the major carbonyl unit, and could be generated by the copolymerization of ethylene with CO formed in situ from cyclopropenone.

Synthesis of Polyethylene with In‐Chain α,β‐Unsaturated Ketone and Isolated Ketone Units: Pd‐Catalyzed Ring‐Opening Copolymerization of Cyclopropenone with Ethylene

Polyolefins with periodic unsaturation in the backbone chain are sought after for synthesizing chemically recyclable polymers or telechelic polyolefin macromonomers. Here we introduce a bottomup synthesis of unsaturated high-density polyethylene (HDPE) via copolymerization of ethylene with dimethyl 7-oxabicyclo[2.2.1]hepta- 2,5-diene-3,5-dicarboxylate followed by post-polymerization retro- Diels-Alder to unveil hidden double bonds in the polymer backbone. The incorporation of this "Trojan Horse" comonomer was varied and a series of unsaturated HDPE polymers with block lengths of 1.2, 1.9, and 3.5 kDa between double bonds was synthesized. Crossmetathesis of unsaturated HDPE samples with 2-hydroxyethyl acrylate yielded telechelic ester terminated PE macromonomers suitable for the preparation of ester-linked PE. These materials were depolymerized and repolymerized, making them suitable candidates for chemical recycling. The ester-linked PE displayed thermal and mechanical properties comparable to commercial HDPE.

Polyethylene Incorporating Diels-Alder Comonomers: A "Trojan Horse" Strategy for Chemically Recyclable Polyolefins.

Aryne intermediates are versatile and important reactive intermediates for natural product and polymer synthesis. 2-Naphthynes are relatively unexplored because few methods provide precursors to these intermediates, especially for those bearing additional substituents. Here we report a general synthetic strategy to access 2-naphthyne precursors through an Asao-Yamamoto benzannulation of ortho-(phenylethynyl)benzaldehydes with halo-silylalkynes. This transformation provides 2-halo-3-silylnaphthalenes with complete regioselectivity. These naphthalene products undergo desilylation/dehalogenation in the presence of F- to generate the corresponding 2-naphthyne intermediate, as evidenced by furan trapping experiments. When these 2-naphthynes are generated in the presence of a copper catalyst, ortho-naphthalene oligomers, trinaphthalene, or binaphthalene products are formed selectively by varying the catalyst loading and reaction temperature. The efficiency, mild conditions, and versatility of the naphthalene products and naphthyne intermediates will provide efficient access to many new functional aromatic systems.

/pdf/rapid-access-to-substituted-2-naphthyne-intermediates-via-5g55r8it8t.pdf

Rapid access to substituted 2-naphthyne intermediates via the benzannulation of halogenated silylalkynes.

Editing of polymer backbones

A palladium-catalyzed alternating copolymerization of [2.2.1]oxabicyclic alkenes 1 with carbon monoxide afforded isomer mixtures of polyketones 2ktn and polyketals 2ktl. Subsequent acid-induced dehydration of polymer 2 furnished novel aromatic polymers consisting of polyketones 3ktn and polyketals 3ktl units. This formal aryne/carbon monoxide copolymerization thus generated the first example of poly(aryne-alt-carbon monoxide)s, in which o-arylene and carbonyl units are incorporated in an alternating fashion.

Formal Aryne/Carbon Monoxide Copolymerization To Form Aromatic Polyketones/Polyketals

As chain-growth polymerization generally forms aliphatic main chains containing units such as alkylene and alkenylene, the method has rarely been applied to the construction of arylene units Thus, the formation/introduction of arylene groups via chain-growth polymerization remains a challenging subject in polymer chemistry In this study, we report a formal aryne/ethylene copolymerization using [221]oxabicyclic alkenes as aryne equivalents A palladium-catalyzed copolymerization of [221]oxabicyclic alkenes with ethylene followed by acid-promoted dehydration produced novel aryne/ethylene copolymers The use of a bulky phosphine–sulfonate ligand was essential to obtain the desired copolymers with high molecular weight We report a formal aryne/ethylene copolymerization using [221]oxabicyclic alkenes as aryne equivalents A palladium-catalyzed copolymerization of [221]oxabicyclic alkenes with ethylene followed by acid-promoted dehydration produced novel aryne/ethylene copolymers The use of a bulky phosphine–sulfonate ligand was essential to obtain the desired copolymers with high molecular weight The present study provides a useful method for the introduction of o-arylene units into the main chains of polyethylene

/pdf/formal-aryne-ethylene-copolymerization-to-form-polyethylene-56g137t5j1.pdf

Formal aryne/ethylene copolymerization to form polyethylene containing o -arylene units in the main chain

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Formal Aryne/Carbon Monoxide Copolymerization To Form Aromatic Polyketones/Polyketals

Formal aryne/ethylene copolymerization to form polyethylene containing o -arylene units in the main chain