Aziridines and azetidines: building blocks for polyamines by anionic and cationic ring-opening polymerization

Gleede, Tassilo; Reisman, Louis; Rieger, Elisabeth; Mbarushimana, Pierre Canisius; Rupar, Paul A.; Wurm, Frederik R.

doi:10.1039/c9py00278b

Cited by 106 publications

(100 citation statements)

References 176 publications

(207 reference statements)

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“…Aziridine/CO ROCOP is an underexplored route towards poly-β-peptides and polypeptoids ( N -alkylated polymer) with potential applications in catalysis, materials and biomedicine 101 – 104 . Suitable catalysis is required to produce poly-β-peptides/polypeptoids and to overcome the formation of side-products such as β-lactams and polyamines (Fig.…”

Section: Ring-opening Polymerisationmentioning

confidence: 99%

Advances in heterometallic ring-opening (co)polymerisation catalysis

2021

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Truly sustainable plastics require renewable feedstocks coupled with efficient production and end-of-life degradation/recycling processes. Some of the most useful degradable materials are aliphatic polyesters, polycarbonates and polyamides, which are often prepared via ring-opening (co)polymerisation (RO(CO)P) using an organometallic catalyst. While there has been extensive research into ligand development, heterometallic cooperativity offers an equally promising yet underexplored strategy to improve catalyst performance, as heterometallic catalysts often exhibit significant activity and selectivity enhancements compared to their homometallic counterparts. This review describes advances in heterometallic RO(CO)P catalyst design, highlighting the overarching structure-activity trends and reactivity patterns to inform future catalyst design.

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Section: Ring-opening Polymerisationmentioning

confidence: 99%

Advances in heterometallic ring-opening (co)polymerisation catalysis

2021

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“…They are widely represented in a variety of biologically active molecules, like nicotianamine (Figure 1) and they have attractive properties for drug design. [5] Azetidines present a reactivity similar to aziridines and can also be used as a starting material for polymer synthesis [6] or as a synthetic precursor for other nitrogen heterocycles. [7] Thietanes (Figure 1) [8] are subunits that are also found in biological structures such as nucleosides [9,10,11].…”

Section: Introductionmentioning

confidence: 99%

Phosphetene: Synthesis and reactivity

Lauwick

Duffy

Bouit

et al. 2021

Coordination Chemistry Reviews

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Four-membered ring heterocycles are less studied than five or six-membered heterocycles. It is even more true for 4-membered P-rings and in particular their unsaturated congeners, namely phosphetenes. In this review, we report the main synthetic strategies developed to prepare such compounds. The study of their reactivity, either in organic transformations or coordination chemistry, illustrates that share both specific reactivities of unsaturated strained cycles and phosphanes making them versatile synthons for original organophosphorus derivatives. Contents 1. Introduction…………………………………………………………………………………………………2 2. Synthesis of phosphetenes……………………………………………………………………………… 4 2.1. via ring expansion…………………………………………………………………………………….4 2.2. via cyclisation of phosphabutadienes………………………………………………………………7 2.3. via [2+2] cycloaddition reactions……………………………………………………………………11 2.4. via intramolecular rearrangement…………………………………………………………………..13 2.5. via addition reaction………………………………………………………………………………….14 2.6. via organometallic intermediates……………………………………………………………………14 3. Reactivity of phosphetenes……………………………………………………………………………….18 3.1. P-reactivity…………………………………………………………………………………………….19 3.2. Ring opening followed by cycloaddition……………………………………………………………20 3.3. Ring expansion…………………………………………………………………………………….…22 4. Conclusion………………………………………………………………………………………………….24

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“… 13 , 16 − 21 They have a significant role as synthetic building blocks of foldamers, 22 , 23 N -heterocycles, 24 − 28 and polymers. 29 It has also been demonstrated, that the introduction of these strained rings improves enormously the fluorescent properties of rhodamines 30 − 32 and coumarins 33 and the efficacy of homogenous catalysts as ligands, 34 , 35 which makes them an attractive and challenging synthetic topic for chemists nowadays. Compared to their widespread uses, there are relatively few synthetic methods available, although they cover a wide range of structural variability.…”

Section: Introductionmentioning

confidence: 99%

Regio- and Diastereoselective Synthesis of 2-Arylazetidines: Quantum Chemical Explanation of Baldwin’s Rules for the Ring-Formation Reactions of Oxiranes

Kovács

Faigl

Mucsi³

2020

J. Org. Chem.

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A general, scalable two-step regio- and diastereoselective method has been described for the synthesis of versatile alkaloid-type azetidines from simple building blocks with excellent overall yields. In the kinetically controlled reaction, only the formation of the strained four-membered ring can be achieved instead of the thermodynamically favorable five-membered rings under appropriate conditions. Remarkable functional group tolerance has also been demonstrated. In this paper, we give a new scope of Baldwin’s rules by density functional theory (DFT) calculations with an explicit solvent model, confirming the proposed reaction mechanisms and the role of kinetic controls in the stereochemical outcome of the reported transition-metal-free carbon–carbon bond formation reactions.

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Aziridines and azetidines: building blocks for polyamines by anionic and cationic ring-opening polymerization

Abstract: The synthesis of aziridine and azetidine monomers and their ring-opening polymerization via different mechanisms is reviewed.

Cited by 106 publications

References 176 publications

Advances in heterometallic ring-opening (co)polymerisation catalysis

Advances in heterometallic ring-opening (co)polymerisation catalysis

Phosphetene: Synthesis and reactivity

Regio- and Diastereoselective Synthesis of 2-Arylazetidines: Quantum Chemical Explanation of Baldwin’s Rules for the Ring-Formation Reactions of Oxiranes

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