Abstract:The
ability to synthesize well-defined block copolymers (BCPs)
from one-pot comonomer mixtures has powerful chemical and practical
implications. However, controlling sequences between highly reactive,
homologous comonomers such as acrylates during polymerization is challenging.
Here we present a Lewis pair polymerization strategy that uniquely
utilizes preferential Lewis acid coordination to differentiate between
comonomers, distinctive kinetics, and compounded thermodynamic and
kinetic differentiation to prec… Show more
“…This ratio can be used as a guiding parameter in designing of FLPs in the future. In recent years, FLPs are being increasingly used in polymerization catalysis [107][108][109], polymer chemistry [110,111], and organic synthesis [112,113] as well.…”
Section: Activation Of Other Small Moleculesmentioning
The chemistry of frustrated Lewis pair (FLP) is widely explored in the activation of small molecules, the hydrogenation of CO2, and unsaturated organic species. A survey of several experimental works on the activation of small molecules by FLPs and the related mechanistic insights into their reactivity from electronic structure theory calculation are provided in the present review, along with the catalytic hydrogenation of CO2. The mechanistic insight into H2 activation is thoroughly discussed, which may provide a guideline to design more efficient FLP for H2 activation. FLPs can activate other small molecules like, CO, NO, CO2, SO2, N2O, alkenes, alkynes, etc. by cooperative action of the Lewis centers of FLPs, as revealed by several computational analyses. The activation barrier of H2 and other small molecules by the FLP can be decreased by utilizing the aromaticity criterion in the FLP as demonstrated by the nucleus independent chemical shift (NICS) analysis. The term boron-ligand cooperation (BLC), which is analogous to the metal-ligand cooperation (MLC), is invoked to describe a distinct class of reactivity of some specific FLPs towards H2 activation.
“…This ratio can be used as a guiding parameter in designing of FLPs in the future. In recent years, FLPs are being increasingly used in polymerization catalysis [107][108][109], polymer chemistry [110,111], and organic synthesis [112,113] as well.…”
Section: Activation Of Other Small Moleculesmentioning
The chemistry of frustrated Lewis pair (FLP) is widely explored in the activation of small molecules, the hydrogenation of CO2, and unsaturated organic species. A survey of several experimental works on the activation of small molecules by FLPs and the related mechanistic insights into their reactivity from electronic structure theory calculation are provided in the present review, along with the catalytic hydrogenation of CO2. The mechanistic insight into H2 activation is thoroughly discussed, which may provide a guideline to design more efficient FLP for H2 activation. FLPs can activate other small molecules like, CO, NO, CO2, SO2, N2O, alkenes, alkynes, etc. by cooperative action of the Lewis centers of FLPs, as revealed by several computational analyses. The activation barrier of H2 and other small molecules by the FLP can be decreased by utilizing the aromaticity criterion in the FLP as demonstrated by the nucleus independent chemical shift (NICS) analysis. The term boron-ligand cooperation (BLC), which is analogous to the metal-ligand cooperation (MLC), is invoked to describe a distinct class of reactivity of some specific FLPs towards H2 activation.
“…Chen pointed out the possibility to activate preferentially one monomer from a mixture of two acrylates to prepare block copolymers without sequential addition of the monomers. [ 355 ] Zhang described a system for the synthesis of sequence‐controlled multiblock copolymers at room temperature. [ 356 ] However, attempts to increase the stereocontrol in LPP of (meth)acrylates at room temperature have not yet been successful.…”
Section: Polymerization Of (Meth)acrylic Monomers and Analogsmentioning
To prepare biobased polymers, particular attention must be paid to the obtention of the monomers from which they are derived. (Meth)acrylates and their analogs constitute such a class of monomers that have been extensively studied due to the wide range of polymers accessible from them. This review therefore aims to highlight the progresses made in the production and polymerization of (meth)acrylates and their analogs. Acrylic acid production from biomass is close to commercialization, as three different high‐potential intermediates are identified: glycerol, lactic acid, and 3‐hydroxypropionic acid. Biobased methacrylic acid is less common, but several promising options are available, such as the decarboxylation of itaconic acid or the dehydration of 2‐hydroxyisobutyric acid. Itaconic acid is also a vinylic monomer of great interest, and polymers derived from it have already found commercial applications. Methylene butyrolactones are promising monomers, obtained from bioresources via three different intermediates: levulinic, succinic, or itaconic acid. Although expensive, methylene butyrolactones have a strong potential for the production of high‐performance polymers. Finally, β‐substituted acrylic monomers, such as cinnamic, fumaric, muconic, or crotonic acid, are also examined, as they provide an original access to biobased materials from various renewable raw materials, such as protein waste, lignin, or wastewater.
“…However, the synthesis of sequence-controlled polypeptides via polymerization is a long-lasting challenge ( Jones, 2008 ; Lutz, 2010 ; Lutz et al., 2013 ). Therefore, a breakthrough in sequence-controlled poly-α/β-peptide synthesis is highly desired, though sequence-controlled polymerizations are reported recently on the synthesis of polyacrylates, polynorbornene, poly(styrene- b -maleimide) and polyesters ( Jia et al., 2021 ; McGraw et al., 2020 ; Pfeifer and Lutz, 2007 ; Yasir et al., 2020 ). Figure 1 Strategies to prepare poly-α/β-peptides (A) Solid-phase synthesis to prepare α/β-peptide oligomers.…”
Summary
The fascinating functions of proteins and peptides in biological systems have attracted intense interest to explore their mimics using polymers, including polypeptides synthesized from polymerization. The folding, structures and functions of proteins and polypeptides are largely dependent on their sequence. However, sequence-tunable polymerization for polypeptide synthesis is a long-lasting challenge. The application of polypeptides is also greatly hindered by their susceptibility to enzymatic degradation. Although poly-α/β-peptide has proven to be an effective strategy to address the stability issue, the synthesis of poly-α/β-peptide from polymerization is not available yet. Hereby, we demonstrate a living and controlled copolymerization on α-NCA and β-NTA to prepare sequence-tunable poly-α/β-peptides. This polymerization strategy shows a prominent solvent-driven characteristic, providing random-like copolymers of poly-α/β-peptides in THF and block-like copolymers of poly-α/β-peptides in a mixed solvent of CHCl
3
/H
2
O (95/5, v/v), and opens new avenues for sequence-tunable polymerization and enables facile synthesis of proteolysis tunable poly-α/β-peptides for diverse applications.
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