A Switchable Domino Process for the Construction of Novel CO₂‐Sourced Sulfur‐Containing Building Blocks and Polymers

Abstract

a-Alkylidene cyclic carbonates (aCCs) recently emerged as attractive CO 2 -sourced synthons for the construction of complex organic molecules.H erein, we report the transformation of aCCs into novel families of sulfur-containing compounds by organocatalyzed chemoselective addition of thiols,f ollowing ad omino process that is switched on/off depending on the desired product. The process is extremely fast and versatile in substrate scope,p rovides selectively linear thiocarbonates or elusive tetrasubstituted ethylene carbonates with high yields following a1 00 %a tom economy reaction, and valorizes CO 2 as arenewable feedstock. It is also exploited to produce al arge diversity of unprecedented functional polymers.I tc onstitutes ar obust platform for the design of new sulfur-containing organic synthons and important families of polymers.Carbon dioxide (CO 2 )i sa na ttractive abundant, safe,a nd renewable carbon source for the synthesis of organic cyclic carbonates.T oday,t hese molecules find many and diverse applications as intermediates for fine chemical synthesis, electrolytes in Li-ion batteries,p olar aprotic solvents,a nd monomers for the preparation of world-relevant polymers such as polycarbonates and polyurethanes. [1] The[ 3 + +2] cycloaddition of CO 2 to epoxides is the most popular and straightforward approach to five-membered cyclic carbonates [2] and, with the recent breakthroughs in their catalyzed transformations, [3] new CO 2 -based organic molecules with ahigh degree of complexity are now accessible. [4] a-Alkylidene cyclic carbonates (aCCs) are also rapidly emerging as another important class of industrially relevant CO 2 -sourced cyclic carbonates. [5] They are produced by catalytic carboxylative coupling of propargylic alcohols with CO 2 . [6] In contrast to the conventional five-membered cyclic carbonates,t he presence of an exocyclic vinylic group facilitates the regioselective ring-opening of the cyclic carbonate by various nucleophiles,l eading to new potentials in modern organic chemistry for the selective construction of novel molecules.The potential of aCCs for the preparation of new building blocks is enormous,b ut examples are still limited to b-oxocarbamates, b-oxocarbonates, b-hydroxy-1,3oxazolidin-2-ones, a-hydroxyketones,a nd 3-dialkylaminooxazolidin-2-ones. [7,8] Recently,s ome of us demonstrated their utility for the synthesis of functional polyurethanes and polycarbonates,o pening new perspectives for the design of advanced materials. [8] Ther ing-opening of aCCs by thiols is potentially attractive to drastically enlarge the scope of these CO 2 -based synthons but is surprisingly unexplored. It is expected to provide new relevant sulfur-containing products for both synthetic organic (e.g. thiocarbonates) and polymer chemistries (e.g.p oly(monothiocarbonates)). Thiocarbonates are notably important synthetic intermediates in organic chemistry [9] and are used as protecting groups for thiols. [10] Poly(monothiocarbonate)s are attractive polymers for optic applications due to the...

Influence of the Cyclic versus Linear Carbonate Segments in the Properties and Performance of CO2-Sourced Polymer Electrolytes for Lithium Batteries

“…The incorporation of the cyclic carbonate moieties within the linear polymer chain is realized by adding a dithiol DT (2,2′-(ethylenedioxy)­diethanethiol) to the organocatalyzed copolymerization of a bis­(α-alkylidene cyclic carbonate) (BisαCC) with polyethylene glycol PEG ( M n = 4000 g/mol) according to a simple one-pot process as illustrated in Scheme . According to previous works, the ring-opening of BisαCC by PEG provides the linear carbonate units, , and the addition of the thiol to BisαCC furnishes the cyclic carbonate one substituted by a thioether group . Various contents of cyclic and linear carbonates were targeted in order to ultimately study the influence of the cyclic carbonate units on the material performances.…”

“…All polymerizations were carried out under identical conditions until full monomer consumption at 25 °C for 24 h by using 5 mol % DBU as a catalyst in DMF. For the sake of comparison, a homopolymer of polycyclic carbonate was prepared according to the same protocol by DBU catalyzed polyaddition of BisαCC with the dithiol DT without PEG following our previously reported strategy . The macromolecular characteristics of the (co)­polymers are summarized in Table .…”

“…Li + and NTf 2 − Diffusivity. The Li + and NTf 2 − diffusivity were measured by 7 Li and 19 F pulsed field gradient nuclear magnetic resonance (PFG-NMR) by using a Bruker spectrometer (300 MHz) at room temperature in DMSO-d 6 . Diffusion measurements were carried out on a 300 MHz Bruker Advance III spectrometer with a Diff50 pulsed field gradient probe and a stimulated echo pulse sequence.…”

Direct Conversion from Carbon Dioxide to Luminescent Poly(β-alkoxyacrylate)s via Multicomponent Tandem Polymerization-Induced Emission

“…10 In many reported works, bis(cyclic carbonate)s (bis-CCs) were firstly prepared from CO 2 and diepoxides, then diamines were introduced to react with bis-CCs via non-regioselective ring opening reactions to obtain poly(hydroxyl urethane)s. [11][12][13] To solve the regioselectivity issue, Detrembleur et al synthesized bis(-alkylidene cyclic carbonate)s (bis-CCs) from CO 2 and bis(propargylic alcohol)s, which could further react with nucleophiles such as diamines, diols and dithiols via regioselective ring opening reactions to generate poly(urethane)s, poly(carbonate)s and poly(thiocarbonate)s, respectively (Scheme 1B). 14,15 Jian et al synthesized a highly reactive trivinyl methacrylate-type monomer from CO 2 and 1,3butadiene via a three-step procedure. Then the monomer was used for the copolymerization with ethylene toward a new class of ester-functionalized polyethylenes (Scheme 1C).…”

CO2-Involved and Isocyanide-based Three-component Polymerization toward Functional Heterocyclic Polymers with Self-assembly and Sensing Properties

“…Generally, the preparation of heterocyclic polymers from CO2-involved polymerizations can be achieved via following two strategies: (1) firstly transforming CO2 into monomers, such as 3ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL) [20][21][22] and five-membered cyclic carbonates (5CC)s; 23,24 (2) directly using CO2 as a monomer. The latter is preferred and elegant works have been done.…”