Novel synthesis of 2-trichloromethyl-4-vinyloxazoline and its derivatization by ring cleavage reactions*

Grigorjeva, Liene; Maļeckis, Ansis; Kļimoviča, Kristīne; Skvorcova, Marija; Ivdra, N.; Leitis, Gundars; Jirgensons, Aigars

doi:10.1007/s10593-012-1077-0

Cited by 10 publications

(6 citation statements)

References 13 publications

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“…While the use of iron chloride is still acceptable within green chemistry, the use of aluminium chloride and dichloromethane should be avoided. The same group could also show that bis(trichloroacetimidate) can serve as starting material for the reaction [ 165 ].…”

Section: Synthetic Applications In Homogeneous Systemsmentioning

confidence: 99%

Organic Synthesis Using Environmentally Benign Acid Catalysis

Kokel

Schäfer

Török

2019

COS

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Recent advances in the application of environmentally benign acid catalysts in organic synthesis are reviewed. The work includes three main parts; (i) description of environmentally benign acid catalysts, (ii) synthesis with heterogeneous and (iii) homogeneous catalysts. The first part provides a brief overview of acid catalysts, both solid acids (metal oxides, zeolites, clays, ion-exchange resins, metal-organic framework based catalysts) and those that are soluble in green solvents (water, alcohols) and at the same time could be regenerated after reactions (metal triflates, heteropoly acids, acidic organocatalysts etc.). The synthesis sections review a broad array of the most common and practical reactions such as Friedel-Crafts and related reactions (acylation, alkylations, hydroxyalkylations, halogenations, nitrations etc.), multicomponent reactions, rearrangements and ring transformations (cyclizations, ring opening). Both the heterogeneous and homogeneous catalytic synthesis parts include an overview of asymmetric acid catalysis with chiral Lewis and Brønsted acids. Although a broad array of catalytic processes are discussed, emphasis is placed on applications with commercially available catalysts as well as those of sustainable nature; thus individual examples are critically reviewed regarding their contribution to sustainable synthesis.

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Section: Synthetic Applications In Homogeneous Systemsmentioning

confidence: 99%

Organic Synthesis Using Environmentally Benign Acid Catalysis

Kokel

Schäfer

Török

2019

COS

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“…8 The oxazoline ring in 4 can be cleaved with HBr to give allylamine derivative 10 (Scheme 5). 8 We have confirmed that these transformations take place with complete conservation of enantiomeric integrity. Scheme 5 Transformation of vinyloxazoline 4 to ring-cleavage products 8-10…”

Section: Scheme 4 Generation Of Carbenium Ion C From Bisimidatementioning

confidence: 99%

“…Vinyloxazoline 4 can be transformed to vinylglycinol 8 under strong acidic hydrolysis conditions 4,8 or to N-trichloroacetylvinylglycinol 9 under milder hydrolytic conditions (Scheme 5). 8 The oxazoline ring in 4 can be cleaved with HBr to give allylamine derivative 10 (Scheme 5). 8 We have confirmed that these transformations take place with complete conservation of enantiomeric integrity.…”

Section: Scheme 4 Generation Of Carbenium Ion C From Bisimidatementioning

confidence: 99%

Unsaturated Amino Alcohols via Cyclization of Allylic Bistrichloroacetimidates

Jirgensons

Grigorjeva

Maļeckis

et al. 2013

Synlett

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In intramolecular allylic substitution of bistrichloroacetimidates, one of the imidate groups can serve as a N-nucleophile while the other can serve as a leaving group, leading to 2-vinyloxazolines. Two approaches based on different mechanisms for allylic substitution can be applied to achieve cyclization of the bisimidates. The reaction, catalyzed by palladium(II), presumably involves aminometalation of the double bond followed by deoxypalladation. Enantioenriched products can be obtained using chiral palladium(II) catalysts as demonstrated for the cyclization of achiral bisimidates derived from (E/Z)-butene-1,4-diol. Allylic substitution can proceed via a competing mechanism that involves carbenium ion formation from a metal-complexed imidate. This enables the use of Lewis acids as nonexpensive and less toxic alternative to palladium catalysts. Regioselectivity of Lewis acid catalyzed bisimidate cyclization is controlled by formation of the most stable carbenium ion as proposed intermediate. This approach provides an efficient access to vinylglycinols, butadienylglycinol, and C-quaternary vinylglycinols.

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“…Polyoxazolines (POx) are among the most tunable family of polymers, with access to readily derivatized 2‐, 4‐, and 5‐substituted monomers allowing an exceptionally broad range of target applications . In addition, functionalization of pendant groups pre‐ or post‐polymerization provide a route to further diversity .…”

Section: Introductionmentioning

confidence: 99%

MALDI-TOF MS investigation of the unconventional termination of living polyoxazoline with ammonia

Kosakowska

Dimitrov²,

Panambur³

et al. 2017

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

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Poly(2‐oxazoline) (POx) based materials have experienced renewed interest, due to their biocompatibility and broad functional diversity. Although research pertaining to cationic ring opening polymerization (CROP) of 2‐oxazoline derivatives spans upwards of 5 decades, modern characterization techniques, specifically Matrix Assisted Laser‐Desorption Ionization—Time of Flight Mass Spectrometry (MALDI‐TOF MS), were not available during early studies to aid in identifying polymer end‐groups. Through careful synthesis and analytical characterization, evidence supports an alternative mode of nucleophilic attack during ammonia termination, with nucleophilic attack occurring at a different site on the terminal oxazolinium than where polymer propagation occurs. Furthermore, investigations employing targeted end‐group modification, in conjunction with MALDI and NMR analysis, determined the structure of the resultant terminal group was a hydroxyethylamino end group. Based on the observed data, a mechanistic explanation for the observed 2‐oxazoline ring‐opening termination is proposed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1303–1312

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Novel synthesis of 2-trichloromethyl-4-vinyloxazoline and its derivatization by ring cleavage reactions*

Cited by 10 publications

References 13 publications

Organic Synthesis Using Environmentally Benign Acid Catalysis

Organic Synthesis Using Environmentally Benign Acid Catalysis

Unsaturated Amino Alcohols via Cyclization of Allylic Bistrichloroacetimidates

MALDI-TOF MS investigation of the unconventional termination of living polyoxazoline with ammonia

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