Termination reaction of living poly(3-hexylthiophene) using thiophene Grignard reagents: Substituent effect on the functionalization

Takagi, Koji; Kawai, Junpei; Kouchi, Ryo

doi:10.1016/j.polymer.2017.04.041

Cited by 3 publications

(4 citation statements)

References 43 publications

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“…However, it sometimes suffers from the instability of the functional initiators derived from the low ability of the coexistence of functional moieties and Ni species. b) Termination method: [ 10,35–42 ] a method involving the reaction between Ni‐Br chain‐end‐functionalized P3HT and a Grignard‐type terminator having a functional group. This method is simple because Ni‐based functional initiators are unnecessary.…”

Section: Methodsmentioning

confidence: 99%

Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex

Inagaki

Yamamoto

Higashihara

2020

Macromol. Rapid Commun.

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and such a breakthrough allows the synthesis of more complicated block copolymers and branched polymers, such as star and graft copolymers, containing P3HT segments with low Ð M values. [13][14][15][16][17][18][19][20][21][22][23][24] Chain-end-functionalized P3HTs, which can also be easily synthesized by such a living polymerization, have received much attention, because the chain-end moiety itself frequently affects device performances in organic electronics. [25][26][27] In addition, chain-end-functionalized P3HTs are used to prepare quantum dots through the coordination between the functional groups and heavy metals. [28] Such quantum dots improve their dispersibility while maintaining a higher conductivity than using normal nonconjugated dispersants. In addition, the chain ends can be used as reactive sites, when synthesizing block and branched copolymers via a crossover reaction, linking reaction, etc. A summary of the synthesis and utilization of chain-end-functionalized P3HTs has been well reviewed elsewhere. [29] Currently, there are three major methods for chain-end functionalization based on the KCTP: a) Initiation method: [30][31][32][33][34] a method using an initiator having a functional group. Since the initiation reaction in a living polymerization is utilized, the quantitative chain-end functionality (Fn) is guaranteed unless the initiation efficiency is incomplete or chain transfer reactions occur. However, it sometimes suffers from the instability of the functional initiators derived from the low ability of the coexistence of functional moieties and Ni species. b) Termination method: [10,[35][36][37][38][39][40][41][42] a method involving the reaction between Ni-Br chain-end-functionalized P3HT and a Grignard-type terminator having a functional group. This method is simple because Ni-based functional initiators are unnecessary. However, excess amounts of the terminators are required to achieve a high functionality. c) Postfunctionalization method: [43][44][45] a method involving site transformation reactions of α-chain-endor ω-chain-end-functionalized polymers. This method is more generalized because various functional groups can be introduced through the precursory chain ends. However, it requires tedious multistep reactions. Each method has advantages and disadvantages, however, method b has been still widely used because of its straightforward strategy. Even when selecting method b, the Grignard reagents having a high basicity must be used in the KCTP method.

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Section: Methodsmentioning

confidence: 99%

Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex

Inagaki

Yamamoto

Higashihara

2020

Macromol. Rapid Commun.

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“…[22][23][24][25] In the termination method, the quasi-living chain end of a polymer is reacted with a functionalized terminator. 26,27 Note that in this method, not only the ω-chain end but also the α,ω-chain ends can be functionalized through a ring-walking system of the nickel catalyst, depending on the types of terminators and catalysts to be used. In the post-modification method, the chain ends are converted to different functional groups after polymerization.…”

Section: Shin Inagaki and Tomoya Higashihara *mentioning

confidence: 99%

Synthesis of an ABC triblock copolymer by a bilateral Click reaction using α,ω-bifunctionalized poly(3-hexylthiophene) as an inner segment

Inagaki

Higashihara

2022

Polym. Chem.

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“…The silylation of heteroarenes can be particularly valuable because the heteroarylsilanes are often more stable than the corresponding heteroarylboronates. 16 We report silylations of five-membered heteroarenes catalyzed by an iridium complex that contains a pyridyl-imidazoline ligand, and also silylationscatalyzed by a recently disclosed complex of 2,9-Me2-phenanthroline (Me2phen). We demonstrate that reactions with these catalysts produce high yields of products that are formed from functionalization of the most sterically accessible C-H bonds of five-membered heteroarenes under conditions in which borylation reactions produce mixtures of products.…”

Section: Figurementioning

confidence: 99%

“…Thus, consistent with prior literature, the products from the borylation of azoles are, in many cases, unstable to air and, in most cases, unstable to silica. 16,18 In contrast, the products from the silylation of azoles 16-23 are stable to air, moisture from solvents stored on the benchtop, and silica. The greater stability of silyl-azoles than of boryl-azoles renders the silylation of the C-H bonds of azoles particularly useful.…”

Section: Table 4 C-h Silylation Of Azoles Amentioning

confidence: 99%

Iridium-Catalyzed Silylation of Five-Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl-Imidazoline Ligand

Karmel¹,

Rubel²,

Kharitonova³

et al. 2019

Preprint

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<div>We report that the silylation of five-membered ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by the combination of</div><div>[Ir(cod)(OMe)]2 and a phenanthroline ligand or a new pyridylimidazoline ligand that further increases the regioselectivity. The silylation reactions with these catalysts produce high yields of heteroarylsilanes from functionalization at the most sterically accessible C–H bonds of these rings under conditions that the borylation of C–H bonds with previously reported catalysts formed mixtures of products or products that are unstable.</div>

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Termination reaction of living poly(3-hexylthiophene) using thiophene Grignard reagents: Substituent effect on the functionalization

Cited by 3 publications

References 43 publications

Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex

Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex

Synthesis of an ABC triblock copolymer by a bilateral Click reaction using α,ω-bifunctionalized poly(3-hexylthiophene) as an inner segment

Iridium-Catalyzed Silylation of Five-Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl-Imidazoline Ligand

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