Novel precision cyclopolymerization of dienes by late transition metal catalysts

TY - JOUR

T1 - Novel precision cyclopolymerization of dienes by late transition metal catalysts

AU - Takeuchi, Daisuke

AU - Park, Sehoon

AU - Okada, Takeshi

AU - Matsuura, Ryuichi

AU - Osakada, Kohtaro

PY - 2007/10

Y1 - 2007/10

N2 - Cycloolefin polymers have attracted much attention because of their high transparency and thermal stability. Late transition metal complexes are found to promote smooth and stereoselective cyclopolymerization of dienes to afford the polymers having cycloalkane groups along the polymer chain. Pd-diimine complexes initiate cyclopolymerization of the dienes to afford polymers containing trans-1,2-disubstituted cyclopentane rings. Use of Pd complexes with a C2-symmetric ligand affords polymers with highly regulated tacticity. Pd-catalyzed copolymerization of dienes with ethylene and α-olefins accompanies quantitative cyclization of each diene unit. 7-Alkyl-1,6-heptadienes undergo the cyclopolymerization with chain walking of the growing polymer catalyzed by the Pd complexes, leading to the polymers with trans-1,2-disubstituted cyclopentane groups located regularly along the linear polymer chain. The Fe and Co complexes with a bis (imino) pyridine ligand promotes the polymerization of unsubstituted 1,6-heptadienes with quantitative cyclization to yield polymers containing five-membered rings. The Fe complex-catalyzed reaction affords the polymers composed of cis-fused five-membered rings, whereas the polymerization using Co catalyst forms the polymers with trans-fused rings.

AB - Cycloolefin polymers have attracted much attention because of their high transparency and thermal stability. Late transition metal complexes are found to promote smooth and stereoselective cyclopolymerization of dienes to afford the polymers having cycloalkane groups along the polymer chain. Pd-diimine complexes initiate cyclopolymerization of the dienes to afford polymers containing trans-1,2-disubstituted cyclopentane rings. Use of Pd complexes with a C2-symmetric ligand affords polymers with highly regulated tacticity. Pd-catalyzed copolymerization of dienes with ethylene and α-olefins accompanies quantitative cyclization of each diene unit. 7-Alkyl-1,6-heptadienes undergo the cyclopolymerization with chain walking of the growing polymer catalyzed by the Pd complexes, leading to the polymers with trans-1,2-disubstituted cyclopentane groups located regularly along the linear polymer chain. The Fe and Co complexes with a bis (imino) pyridine ligand promotes the polymerization of unsubstituted 1,6-heptadienes with quantitative cyclization to yield polymers containing five-membered rings. The Fe complex-catalyzed reaction affords the polymers composed of cis-fused five-membered rings, whereas the polymerization using Co catalyst forms the polymers with trans-fused rings.

KW - Chain-walking reaction

KW - Co complex

KW - Cyclocopolymerization

KW - Cycloolefin polymer

KW - Cyclopolymerization

KW - Fe complex

KW - Non-conjugated diene

KW - Pd complex

UR - http://www.scopus.com/inward/record.url?scp=36248992322&partnerID=8YFLogxK

U2 - 10.1295/koron.64.597

DO - 10.1295/koron.64.597

M3 - 文章

AN - SCOPUS:36248992322

SN - 0386-2186

VL - 64

SP - 597

EP - 606

JO - Kobunshi Ronbunshu

JF - Kobunshi Ronbunshu

IS - 10

ER -