ADMET Polymerization of Amino‐Acid‐Based Diene

Abstract

1,4‐Di(homo)allyl‐2,5‐diketopiperazines are synthesized and polymerized via ADMET using the Hoveyda–Grubbs 2nd generation catalyst. The but‐3‐enylated diketopiperazine can be converted into unsaturated tertiary polyamide with molar mass of <3000 g mol−1, whereas the allylated diketopiperazine cannot. Double‐bond isomerization occurs regardless of whether or not benzoquinone is present. A polyesteramide with a higher molar mass of ca. 4800 g mol−1 is obtained by the alternating copolymerization (ALTMET) of 1,4‐di(but‐3‐enyl)‐2,5‐diketopiperazine and ethylene glycol diacrylate. A post‐polymerization modification of the poly(ester)amides via radical thiol‐ene chemistry, however, fails.

Synthesis of Poly(vitamin C) through ADMET

“…From the table, it is clear that the polymers with moderate molecular weight were obtained when the polymerization was conducted under bulk conditions employing Grubbs first generation catalyst (G1) or Hoveyda–Grubbs second generation catalyst (HG‐2). Surprisingly, polymers with higher molecular weights and yields were achieved when the G1 was employed as the polymerization catalyst with respect to the HG‐2, although HG‐2 has been the most studied catalyst for the ADMET polymerization of the bio‐related structures . In the solution case, on the other hand, polymers with low molecular weights were achieved regardless of the catalyst type.…”

“…ADMET polymerization of compounds possessing biological importance has gained significant interest in recent years. For instance, a variety of amino acid, peptide, plant oil, and fatty acid derivatives have been smoothly polymerized through ADMET . It should be noted here that since none of those biological molecules originally include α,ω‐diene structure, some chemical modifications have been performed to convert those compounds into a polymerizable monomer.…”

Integrating plant oils into thermally curable main-chain benzoxazine polymers via ADMET polymerization

“…The ADMET polymerization of the BzD monomer was initially investigated using the HG-2 catalyst because has demonstrated notorious tolerance and activity toward coordinative and non-coordinative heteroatom-containing dienes (Table 1) [35,[39][40][41]. ADMET reactions were run for 15h at 50ºC in absence of solvent and under vacuum to remove the released ethylene.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…108) [418]; (10) linkage through a diketopiperazine nucleus (e.g. 109) [419]; (11) linkage through the N and α-carbonyl positions of Ugi-derived α-amino acid derivatives [420]; (12) linkage through a bis(amide) group (e.g. 110) [421]; (13) linkage through a oxa-or thiazolidine nucleus (e.g.…”