Chiral Polyolefins Bearing Amino Acids

Unsaturated PA X,20 from Renewable Resources via Metathesis and Catalytic Amidation

“…[6] Due to the development of functional group tolerant metathesis catalysts, it is now possible to polymerize various a,v-dienes bearing ether, ester, ketone, acetal, alcohol, amino acid, boronate, and carboxylic acid functional groups via ADMET polymerization. [7][8][9][10][11][12][13][14] However, attempts to polymerize amide containing a,v-dienes were less successful until now. Tastard et al described the indirect polymerization of a variety of amide containing a,v-dienes by first performing a ring-closing metathesis (RCM) reaction at high dilution in chloroform or THF with 1 mol-% of the Grubbs second generation catalyst to obtain an amide containing macrocycle in moderate to good yields.…”

Bio-olefins via condensation metathesis chemistry

“…We have recently reported the polymerization of various protected amino acid/peptide branched dienes, yielding polyolefins, termed bio-olefins, as further examples of the functional group tolerance of the second generation Grubbs' catalyst 1a [33][34][35][36][37][38][39]. Further, the molecular weights obtained by ADMET polymerizations resemble those obtained by typical polycondensation reactions e.g.…”

“…To investigate the polymerizability of amino acid branched monomers, the smallest chiral amino acid (alanine) branched dienes were prepared first [33,37,38]. To our delight, all of the alanine branched polymers (9a-9f) were prepared in high molecular weight (Table 1).…”

“…n = 3, R = CH 3 , PG = BOC 4d) n = 8, R = CH 3 , PG = BOC 4e) n = 8, R = CH 3 , PG = CBz 4f) n = 9, R = CH 3 , PG = BOC 5f) n = 3, R = CH 2 CH(CH 3 ) 2 , PG = BOC 5g) n = 9, R = CH 2 CH(CH 3 ) 2 , PG = BOC 6c) n = 3, R = (CH 2 ) 4 NHBOC, PG = BOC 6d) n = 8, R = (CH 2 ) 4 NHBOC, PG = BOC 6e) n = 9, R = (CH 2 ) 4 NHCBz, PG = CBz 6f) n = 9, R = (CH 2 ) 4 NHBOC, PG = BOC 8) n = 3, R = CH 3 , PG = BOC 9d) n = 8, R = CH 3 , PG = BOC 9e) n = 8, R = CH 3 , PG = CBz 9f) n = 9, R = CH 3 , PG = BOC 10f) n = 3, R = CH 2 CH(CH 3 ) 2 , PG = BOC 10g) n = 9, R = CH 2 CH(CH 3 ) 2 , PG = BOC 11c) n = 3, R = (CH 2 ) 4 NHBOC, PG = BOC 11d) n = 8, R = (CH 2 ) 4 NHBOC, PG = BOC 11e) n = 9, R = (CH 2 ) 4 NHCBz, PG = CBz 11f) n = 9, R = (CH 2 ) 4 NHBOC, PG = BOC 13) n = 9, R = CH 2 SCBz, PG = CBz 1a or 1b Illustration of the amino acid branched polymers prepared to date[33][34][35][36][37][38][39]. Explanation of numbering system: (4/9) alanine branched monomers/polymers, (5/10) leucine branched monomers/polymers, (6/11) lysine branched monomers/polymers, (7/12) arginine branched monomer/polymer, and (8/13) cysteine branched monomer/polymer (note stereocenter for 8/13 is R not S).…”

Synthesis and Chiroptical Properties ofL‐Serine‐Based Poly(phenylacetylenes)

“…Grubbs and coworkers (12,13) and North and coworkers (14) have synthesized poly(norbornenes) bearing amino acids and peptides by ring-opening metathesis polymerization. Wagener and coworkers have synthesized amino acidand dipeptide-branched polyolefins by acyclic diene metathesis polycondensation (15)(16)(17).…”