Hydrogen‐Bonding Catalysts Based on Fluorinated Alcohol Derivatives for Living Polymerization

Coulembier, Olivier; Sanders, Daniel P.; Nelson, Alshakim; Hollenbeck, Andrew N.; Horn, Hans W.; Rice, Julia E.; Fujiwara, Masaki; Dubois, Philippe; Hedrick, James L.

doi:10.1002/ange.200901006

Cited by 91 publications

(19 citation statements)

References 33 publications

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“…Another efficient “multiple reversible noncovalent activating” system was elaborated by Hedrick et al using a bimolecular system composed of (−)‐sparteine (SP) and fluorinated tertiary alcohols (FtAs) . In such a concept, the bulky electron‐withdrawing fluorinated groups of FtA serve to increase the acidity of the initiating/propagating alcohol, whereas steric factors reduce the nucleophilicity of the FtA and prevent their participation in the initiation or chain‐transfer reactions.…”

Section: Cationic and Supramolecular Activated Metal‐free Rops Of β‐Lmentioning

confidence: 99%

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

Khalil

Cammas‐Marion

Coulembier

2019

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

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Organocatalysis offers a number of prospects in the polymer community and presents advantages over metal based and bio‐organic methods. The use of organic molecules for performing chemical reactions is not a new concept, and any research into organocatalytic reactions builds on a respected history. Compared to the organocatalysis of large lactones, which began in the early 2000s, the examples presented here will demonstrate that few metal‐free initiating systems had been applied to β‐lactones well before the beginning of the current millennium. These metal‐free initiating systems present indisputable advantages over metal‐based processes. In the following paper, ring‐opening polymerizations (ROPs) of various β‐lactones for the preparation of poly(hydroxyalkanoate)s will be presented, as will the types of mechanisms involved, that is, zwitterionic and anionic, and cationic or supramolecular‐based ROPs. The advantages and drawbacks of the different technics will be discussed in the domain, which, for us, is important in the overall production of bioplastics. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 657–672

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Section: Cationic and Supramolecular Activated Metal‐free Rops Of β‐Lmentioning

confidence: 99%

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

Khalil

Cammas‐Marion

Coulembier

2019

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

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“…The strategies encompass the activation of the monomer, that is, the electrophile (using Brønsted acids, [3] alcohols, [4] 4-dimethylaminopyridine (DMAP) derivatives, [5] phosphines, [6] N-heterocyclic carbenes [7] ); the activation of the growing polymer chain, that is, the nucleophile (using basic phosphazenes, [8] 1,8-diazabicycloA C H T U N G T R E N N U N G [5. 4.0]undec-7-ene (DBU), and 7-methyl-1,5,7-triazabicycloA C H T U N G T R E N N U N G [4.4.0]dec-5-ene (MTBD) [9] ); or the dual activation of both monomer and chain end (thiourea derivatives [10] and 1,5,7-triazabicyclo-A C H T U N G T R E N N U N G [4.4.0]dec-5-ene (TBD) [11] ). Among the organocatalysts, thioA C H T U N G T R E N N U N G ureas [12] have shown promising results in the access of polymers with controlled molar masses, operating under mild conditions (20 8C, loading of catalyst below 10 mol %).…”

Section: Introductionmentioning

confidence: 99%

(Thio)Amidoindoles and (Thio)Amidobenzimidazoles: An Investigation of Their Hydrogen‐Bonding and Organocatalytic Properties in the Ring‐Opening Polymerization of Lactide

Koeller

Kadota

Peruch

et al. 2010

Chemistry A European J

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The mechanism of the ring-opening polymerization (ROP) of lactide catalyzed by two partner hydrogen-bonding organocatalysts was explored. New amidoindoles 4 a,c, thioamidoindoles 4 b,d, amidobenzimidazoles 5 a,c, and thioamidobenzimidazoles 5 b,c were synthesized and used as activators of the monomer. In the solid state and in solution, compounds 4 and 5 showed a propensity for self-association, which was evaluated. (Thio)Amides 4 and 5 do catalyze the ROP of lactide in the presence of a cocatalyst, tertiary amine 3 a or 3 b, which activates the growing polymer chain through hydrogen-bonding. Reactions were conducted in 2-24 h at 20 degrees C; conversion yields ranged between 22 and 100 %. A detailed study of the intermolecular interactions undertaken between the participating species showed that, as expected, simultaneous weak hydrogen bonds do exist to activate the reagents. Moreover, interactions have been revealed between the partner catalysts 4/5+3. ROP catalyzed by these partner activators is thus governed by multiple dynamic equilibria. The latter should be judiciously adjusted to fine-tune the catalytic properties of (thio)amides and organocatalysts, more generally.

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“…Particular attention has been devoted to support the cooperative dual hydrogen‐bonding activation of the monomer by the bis‐sulfonamide. During the preparation of this manuscript, Dubois and coworkers reported the use of fluorinated bis‐alcohols (as dual hydrogen bond donors) in combination with sparteine for the ROP of lactide, β‐butyrolactone and a functionalized trimethylene carbonate 14…”

Section: Introductionmentioning

confidence: 99%

Controlled ring‐opening polymerization of lactide by bis‐sulfonamide/amine associations: Cooperative hydrogen‐bonding catalysis

Alba

Schopp

Delgado

et al. 2010

J. Polym. Sci. A Polym. Chem.

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The bis‐sulfonamide m‐C6H4(SO2NHPh)2 efficiently promotes the ring‐opening polymerization of lactide when combined with tertiary amines, such as N,N‐dimethylaminopyridine. Polylactides of controlled molecular weights (Mn up to 17,700 g mol−1) and very narrow molecular weight distributions (Mw/Mn < 1.11) are obtained under mild conditions and in a living fashion. The reaction takes place through a bifunctional mechanism involving activation of both the alcohol and the monomer. Modulation of the sulfonamide component supports cooperative dual hydrogen‐bonding of lactide involving the two (SO2NHAr) moieties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 959–965, 2010

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Hydrogen‐Bonding Catalysts Based on Fluorinated Alcohol Derivatives for Living Polymerization

Cited by 91 publications

References 33 publications

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

Organocatalysis applied to the ring‐opening polymerization of β‐lactones: A brief overview

(Thio)Amidoindoles and (Thio)Amidobenzimidazoles: An Investigation of Their Hydrogen‐Bonding and Organocatalytic Properties in the Ring‐Opening Polymerization of Lactide

Controlled ring‐opening polymerization of lactide by bis‐sulfonamide/amine associations: Cooperative hydrogen‐bonding catalysis

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