Matthew R. Giles

Living ring-opening metathesis polymerisation of amino ester functionalised norbornenes

The living ring-opening metathesis polymerisation of norbornene monomers bearing amino ester- residues, using the molybdenum initiators Mo(=CHCMe2Ph)(=N?2,6-i-Pr2C6H3)(OR)2, {R = CMe3, IA, CMe2CF3, IB, CMe(CF3)2, IC}, is reported. The monomers are derived from reactions of exo- and endo- himic anhydrides with the amino ester hydrochlorides of glycine (1), alanine (2) and isoleucine (3). The optically pure monomers derived from 2 and 3 afford optically active polymers whose optical activities are independent of cis content and molecular weight, indicating the absence of a cooperative effect between chiral centres along the chain. The polymers derived from the exo monomers show a cis-trans vinylene dependence upon the ancillary alkoxide ligands of the initiator with IA giving high trans contents and IC giving high cis. The cis/trans content for the endo polymers show relatively little or no dependence upon the initiator. Poly(exo-1) is exceptional in its ability to incorporate various hydrocarbons in the solid state, including hexane and methane.

Ruthenium initiated ring opening metathesis polymerisation of amino-acid and -ester functionalised norbornenes and a highly selective chain-end functionalisation reaction using molecular oxygen

Abstract [Ru( CHPh)(PCy 3 ) 2 Cl 2 ] is shown to initiate the living ring opening metathesis polymerisation of amino-acid and -ester functionalised norbornenes; treatment of the living polymers with molecular oxygen gives rise to a highly selective chain-end functionalisation reaction.

Alkene metathesis in the synthesis of novel β-lactams

Both monocyclic and bicyclic β-lactams systems are prepared via alkene metathesis reactions using Mo(CHC-Me2Ph)(NC6H3Pr2i-2,6)[OCMe(CF3)2]2 or Ru(HPh)-Cl2(PCy3)2.

Synthesis of penicillin derived polymers utilising ring-openingmetathesis polymerisation methodology

Penicillin functionalised poly(norbornene)s are synthesised via living ring-opening metathesis polymerisation using the ruthenium initiator {RuCl 2 (CHPh)[P(C 6 H 11 ) 3 ] 2 }.

Tandem asymmetric allylboration–alkene metathesis: a novel strategy for the synthesis of trans-disubstituted homoallylic alcohols

Tandem use of Browns asymmetric allylboration technology and crossed-alkene metathesis provides exclusively trans-disubstituted homoallylic alcohols in good yields.

The synthesis and ring-opening metathesis polymerization of peptide functionalized norbornenes

Norbornene monomers bearing two and three amino acid residues have been synthesized and the ring-opening metathesis polymerization of the monomers investigated using Mo(CHCMe2Ph)(N-2,6-Pri2C6H3)(OR)2, [R = CMe3 1a, CMe2CF3 1b, CMe(CF3)2 1c].

Highly functionalised monocyclic and bicyclic β-lactamsvia alkene metathesis

Both monocyclic and bicyclic β-lactam systems are prepared via alkene metathesis reactions using Mo(CHCPhMe 2 )- (NC 6 H 3 Pr i 2 )[(OCMe(CF 3 ) 2 ] 2 or Ru(CHPh)Cl 2 (PCy 3 ) 2 .