A General Protocol for the Polycondensation of Thienyl <i>N</i>-Methyliminodiacetic Acid Boronate Esters To Form High Molecular Weight Copolymers

Carrillo, Josué Ayuso; Turner, Michael L.; Ingleson, Michael J.

doi:10.1021/jacs.6b07666

Cited by 23 publications

(18 citation statements)

References 48 publications

(81 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…137 This mechanistic divergence is consistent with extensive reaction kinetics, kinetic isotope effects, 18 O labelling, and computational data. In-situ slow release of MIDA boronates has been advantageous for many reactions including couplings of unstable heteroarylboronates, 138,139 polymerization reactions, 140–141 asymmetric methodologies, 142 the synthesis of organic photovoltaics, 143 and a one-pot homologation of boronic acids. 144 …”

Section: Advances Towards a General Platform For Iterative Small Molementioning

confidence: 99%

See 1 more Smart Citation

Towards the generalized iterative synthesis of small molecules

2018

View full text Add to dashboard Cite

Small molecules have extensive untapped potential to benefit society, but access to this potential is too often restricted by limitations inherent to the customized approach currently used to synthesize this class of chemical matter. In contrast, the “building block approach”, i.e., generalized iterative assembly of interchangeable parts, has now proven to be a highly efficient and flexible way to construct things ranging all the way from skyscrapers to macromolecules to artificial intelligence algorithms. The structural redundancy found in many small molecules suggests that they possess a similar capacity for generalized building block-based construction. It is also encouraging that many customized iterative synthesis methods have been developed that improve access to specific classes of small molecules. There has also been substantial recent progress toward the iterative assembly of many different types of small molecules, including complex natural products, pharmaceuticals, biological probes, and materials, using common building blocks and coupling chemistry. Collectively, these advances suggest that a generalized building block approach for small molecule synthesis may be within reach.

show abstract

Section: Advances Towards a General Platform For Iterative Small Molementioning

confidence: 99%

“…4–5 MIDA boronates have been employed independent of iteration on a wide range of other small molecule synthesis applications as well. 140–141, 143, 150, 180, 186–193 …”

Section: Iterative Cross-coupling With Mida Boronatesmentioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

View full text Add to dashboard Cite

show abstract

“…Suzuki-Miyaura polymerisation of 1 displayed reaction features analogously to other MIDA boronate esters, e.g., slow release of the corresponding thienyl boronic acid, step-growth of polymer chains over time, high yield and high molecular weight of isolated polymer. For example, Figure 1 shows the increase of polymer molecular weights of pCPDT over time (Ayuso Carrillo et al, 2015;2016;Foster et al, 2017). Likewise, the 1 H NMR spectra of the filtered solutions after polymer precipitation ( Figure S1) showed evidence of 1 only but no deboronated monomer, after 4 h and 8 h of reaction.…”

Section: Resultsmentioning

confidence: 93%

Cyclopentadithiophene polymers synthesised via Suzuki-Miyaura polymerisation of MIDA boronate esters

Carrillo

Feng

2020

Exp Results

View full text Add to dashboard Cite

Cyclopentadithiophene (CPDT), a Csp3-bridged bithiophene heteroaromatic unit, displays interesting properties when it is embedded in the repeating units of π-conjugated polymers, and they are applied in organic electronics devices. Common synthetic routes to CPDT-derived polymers rely on toxic methodologies whilst alternative non-toxic strategies such as the Suzuki-Miyaura reaction have been less studied. In this report we demonstrate that the use of a N-methyliminodiacetic acid (MIDA) boronate ester-derived CPDT monomer allows the efficient formation of poly(cyclopentadithiophene) homopolymer under Suzuki-Miyaura cross-coupling reaction conditions. Thus, the use of MIDA boronate esters might be extended to other organic units to design and construct a plethora of π-conjugated polymers.

show abstract

“…Hydrolysis of the BMIDA moiety by water under neutral conditions has been observed for a range of aryl‐ and heteroaryl‐BMIDA boronate esters . To understand the species involved in the Suzuki‐Miyaura reaction, the hydrolysis of monomer 1b was studied in THF/water mixtures.…”

Section: Resultsmentioning

confidence: 99%

“…This process produced MIDA boronate esters without requiring the synthesis and isolation of arylboronic acid intermediates, some of which can be particularly susceptible to protodeboronation . The slow hydrolysis of thienyl bis MIDA boronate ester (AA type) monomers has most recently been used in Suzuki‐Miyaura copolymerizations to produce a range of thiophene containing polymers (Scheme ) …”

Section: Introductionmentioning

confidence: 99%

Use of N‐methyliminodiacetic acid boronate esters in suzuki‐miyaura cross‐coupling polymerizations of triarylamine and fluorene monomers

Foster

Bagutski

Carrillo

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

Self Cite

View full text Add to dashboard Cite

Polytriarylamine copolymers can be prepared by Suzuki‐Miyaura cross‐coupling reactions of bis N‐methyliminodiacetic acid (MIDA) boronate ester substituted arylamines with dibromo arenes. The roles of solvent composition, temperature, reaction time, and co‐monomer structure were examined and (co)polymers prepared containing 9, 9‐dioctylfluorene (F8), 4‐sec‐butyl or 4‐octylphenyl diphenyl amine (TFB), and N, N′‐bis(4‐octylphenyl)‐N, N′‐diphenyl phenylenediamine (PTB) units, using a Pd(OAc)2/2‐dicyclohexylphosphino‐2′,6′‐dimethoxybiphenyl (SPhos) catalyst system. The performance of a di‐functionalized MIDA boronate ester monomer was compared with that of an equivalent pinacol boronate ester. Higher molar mass polymers were produced from reactions starting with a difunctionalized pinacol boronate ester monomer than the equivalent difunctionalized MIDA boronate ester monomer in biphase solvent mixtures (toluene/dioxane/water). Matrix‐assisted laser desorption/ionization mass spectroscopic analysis revealed that polymeric structures rich in residues associated with the starting MIDA monomer were present, suggesting that homo‐coupling of the boronate ester must be occurring to the detriment of cross‐coupling in the step‐growth polymerization. However, when comparable reactions of the two boronate monomers with a dibromo fluorene monomer were completed in a single phase solvent mixture (dioxane + water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2798–2806

show abstract

A General Protocol for the Polycondensation of Thienyl N-Methyliminodiacetic Acid Boronate Esters To Form High Molecular Weight Copolymers

Cited by 23 publications

References 48 publications

Towards the generalized iterative synthesis of small molecules

Towards the generalized iterative synthesis of small molecules

Cyclopentadithiophene polymers synthesised via Suzuki-Miyaura polymerisation of MIDA boronate esters

Use of N‐methyliminodiacetic acid boronate esters in suzuki‐miyaura cross‐coupling polymerizations of triarylamine and fluorene monomers

Contact Info

Product

Resources

About