Modified Poly(ε-caprolactone)s: An Efficient and Renewable Access via Thia-Michael Addition and Baeyer–Villiger Oxidation

Winkler, Mathias; Raupp, Yasmin S.; Köhl, Lenz A. M.; Wagner, Hanna E.; Meier, Michael A. R.

doi:10.1021/ma500381n

Cited by 35 publications

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“…To synthesize the modified caprolactam monomers, different thiols were used to prepare modified cyclohexanones 3a–c via thia‐Michael addition (see Figure for complete synthesis procedure). The thia‐Michael addition was highly suitable to modify 1‐cyclohex‐2‐enone 1 , as already described recently . With a slight excess of the thiols 2a–c (1.20 equivalents), the products could be obtained at a temperature of 50 °C in quantitative yields under solvent‐free conditions using triethylamine as catalyst.…”

Section: Resultsmentioning

confidence: 79%

Synthesis of Modified Polycaprolactams Obtained from Renewable Resources

Oelmann

Meier

2015

Macromol. Chem. Phys.

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Modified caprolactam monomers, derived from renewable resources, are prepared to obtain novel polyamides with tunable properties. Starting from 2‐cyclohex‐1‐enone, a thia‐Michael addition is used as key step to synthesize modified monomer precursors. The monomer synthesis is optimized in order to achieve high yields utilizing environmentally benign synthesis procedures. The modified caprolactam monomers are obtained with high regioselectivity via the Beckmann rearrangement of the prepared cyclohexanone oximes. Using tin(II)2‐ethylhexanoat (Sn(Oct)2) as catalyst, it is possible to obtain the modified polycaprolactams in good yields. It is noteworthy that for the synthesis of the regioselective caprolactam monomers, the use of toxic reagents is avoided and the generation of waste is minimized in order to meet the requirements for environmentally benign synthesis procedures.

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Section: Resultsmentioning

confidence: 79%

Synthesis of Modified Polycaprolactams Obtained from Renewable Resources

Oelmann

Meier

2015

Macromol. Chem. Phys.

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“…[66][67][68] In 2005, Zanda and co-workers realized the first efficient and enantioselective synthesis of g-trifluoromethyl-g-sulfone hydroxamates 46 under mild conditions (Scheme 35). [69] In the first step, ad iastereomeric mixture of thia-Michael adducts was obtained by reacting (S,E)-4-benzyl-3-(4,4,4-trifluorobut-2-enoyl)oxazolidin-2-one (41)w ith 4-methoxybenzenethiol (2)i nE t 3 N/CH 2 Cl 2 at ambient temperature. This diastereomeric mixture of thia-Michael adducts was separated by flash columnc hromatographya nd the required diastereomer was subsequently converted into the corresponding g-trifluoromethyl-g-sulfone hydroxamate (46)i nt hree steps in 80 % overall yield.…”

Section: Scheme29 K 3 Po 4 -Mediated Thia-michael Addition Reactionmentioning

confidence: 99%

Thia‐Michael Addition: An Emerging Strategy in Organic Synthesis

2018

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The thia-Michael addition reactionh as been demonstrated to be ah ighly powerful tool in organic synthesis. Indeed, the influential natureo ft his reactionh as been wellestablished in the fields of medicinal chemistry,c atalysis, drug discovery,a nd materials science. The emergence of numerous synthetic strategies that take advantage of thia-Michael addition reactions of electron-deficienta lkenes has unleashed countless opportunities for the design and synthesis of diverse biologically relevant organosulfurc ompounds. However,d espite myriad potential synthetic applications, there has not been anye xclusive reviewso ft he thia-Michael addition reaction. Therefore, this Focus Review plots the journeyo ft he thia-Michael addition reaction in organic synthesis, and is categorized according to catalyzed and catalyst-free thia-Michael addition reactions. Figure 1. Summary of the applicationsoft hia-Michael adducts.[a] Dr.Scheme1.Catalyzed pathways for the thia-Michael addition reaction.EW-G = electron-withdrawing group.Scheme2.Acetic-acid-catalyzed thia-Michael additionr eaction proposed by Allen et al. [24] AsianJ.O rg.Scheme3.Indium-bromide-catalyzed thia-Michael addition reaction.Scheme4.Thia-Michael addition reaction followed by a1 ,2-addition of TMSCN in one pot. TMSCN = trimethylsilyl cyanide.Scheme5.Bi III -catalyzedt hia-Michael additionreactiono fa,b-unsaturated carbonyl compounds. Tf = trifluoromethanesulfonyl.Scheme6.Bismuth-triflate-catalyzed synthesis of bis-thioether compounds. Bn = benzyl.Scheme7.Iron-/copper-catalyzed thia-Michael additionr eaction.Scheme8.VO(OTf) 2 -mediated synthesis of b-mercapto ketones. Np = naphthyl.Scheme9.Substrate scope for the synthesis of 3-sulfanyl-substituted 1-(arylamino)-pyrrolidine-2,5-diones.Scheme10. Regio-and enantioselective addition at the d position of conjugated systems.Scheme11. Mechanistic modelf or the enantioselective d addition of at hiol to an a,b,g,d-unsaturated dienone,catalyzed by achiral Fe III Àsalenc omplex.Scheme12. Chemoselectivesynthesis of 2-amino-3,1-benzothiazines (15) and 3,4-dihydroquinazoline-2-thiones (16)byu sing ortho-aminocinnamate (13)a nd isothiocyanates 14.Scheme13. Reactionmechanism for the chemoselective synthesis of 2amino-3,1-benzothiazines (15)and 3,4-dihydroquinazoline-2-thiones (16).Scheme14. ZrCl 4 -assisted three-component reactionf or the synthesiso fbaryl-b-mercapto ketones.Scheme15. LiF-nanocube-mediated thia-Michael addition reaction.Scheme57. Ni II -catalyzed enantioselective synthesiso f2-aryl-3-nitrothiochroman-4-ols.Scheme58. Te ntative reaction mechanism for the Ni II -catalyzed asymmetric synthesis of 2-aryl-3-nitrothiochroman-4-ols.Scheme59. Pepsin-catalyzed synthesis of functionalized chiral dihydrothiophenes.Scheme69. Mechanistic aspects of the stereoselectives ynthesis of tetrahydrothioxanthenones.Scheme70. Enantioselectivesynthesis of methyl 2-((R)-2-nitro-1-(aryl/heteroaryl)ethylthio)acetatesa nd thiomorpholin-3-ones.Scheme71. Water-accelerated thia-Michael additionr eaction proposedb y Chakraborti and co-work...

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“…In the presence of a catalytic amount of Et 3 N, thia-Michael addition of RSH to conjugated cyclohexenone was accomplished. 15 Thioboration of α,β-unsaturated ketones and aldehydes gave vinylborate analogues having a sulfide bond at the β-position, even without any base or metal. 16 To quinones, a silver-catalyzed addition of diphenyl disulfide (PhSSPh) was reported (Scheme 4a).…”

Section: As Representative Anionic Sulfur-containing Species Rsmentioning

confidence: 99%

Emerging Organosulfonium Electrophiles as Unique Reagents for Carbon–Sulfur Bond Formation: Prospects in Synthetic Chemistry of Organosulfur Compounds

Aida

Oyaizu

2016

Chem. Lett.

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Carbonsulfur (CS) bond formation is one of the important synthetic routes in organic chemistry. Among sulfur sources for CS bond formation, organosulfur cations (RS + ) and their synthetic equivalents are unique reagents. These cationic sulfur species are easily prepared as compared with the oxonium analogues, because of their low ionization potentials. This review describes various synthetic methods for CS bond formation, mainly focusing on electrophilic reactions, addition to olefins, and substitution to aromatic rings. A breakthrough has been anticipated for RS + electrophiles, based on their versatile utility in aromatic polymer synthesis.

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Modified Poly(ε-caprolactone)s: An Efficient and Renewable Access via Thia-Michael Addition and Baeyer–Villiger Oxidation

Cited by 35 publications

References 36 publications

Synthesis of Modified Polycaprolactams Obtained from Renewable Resources

Synthesis of Modified Polycaprolactams Obtained from Renewable Resources

Thia‐Michael Addition: An Emerging Strategy in Organic Synthesis

Emerging Organosulfonium Electrophiles as Unique Reagents for Carbon–Sulfur Bond Formation: Prospects in Synthetic Chemistry of Organosulfur Compounds

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