Bifunctional [c2]Daisy-Chains and Their Incorporation into Mechanically Interlocked Polymers
摘要:
A strategy for the formation of mechanically interlocked polymers is presented. Ring-closing olefin metathesis has been shown to provide a very high yielding route to [c2]daisy-chains suitably functionalized to allow their one-step conversion to bisolefins which can be used as monomers in ADMET polymerizations to afford mechanically interlocked polymers. Metathesis, in two different guises is making a hitherto unreachable goal in synthesis a reality.
Synthesis of Small and Large Fused Bicyclic Compounds by Tandem Dienyne Ring-Closing Metathesis
作者:Hyeon Park、You-Lee Hong、Yongjoo B. Kim、Tae-Lim Choi
DOI:10.1021/ol101233k
日期:2010.8.6
A tandem ring-closing metathesis reaction using ruthenium catalyst was carried out to synthesize various fused bicyclic compounds containing both small and large rings. Fast ring-closure of the small ring and slow ring-closure of the large ring resulted in the formation of only one Isomer. Further manipulation such as the Diels-Alder reaction was carried out to prepare a complex molecule containing multiple rings of different sizes.
Switching and Extension of a [c2]Daisy-Chain Dimer Polymer
作者:Paul G. Clark、Michael W. Day、Robert H. Grubbs
DOI:10.1021/ja905924u
日期:2009.9.30
We report the synthesis of a [c2]daisy-chain dimer via ruthenium-catalyzed ring-closing olefin metathesis. Confirmation of the interlocked nature of the structure was achieved through single-crystal X-ray diffraction analysis. The dimer could be readily switched from the bound to the unbound conformation by treatment with 3.0 equiv of KOH and subsequently reprotonated by treatment with 3.0 equiv of HPF6. Azide functionalization of the dimer enabled incorporation in linear step-growth polymer chains using the alkyne-azide "click" reaction. Get permeation chromatography coupled with multiangle laser light scattering analysis showed the polymers contained 22 dimers and had a radius of gyration of 14.8 nm. Acylation of the amines of the dimers sterically forced elongation of the interlocked units, and MALLS analysis of the polymer showed a 48% increase in the R-s (21.4 nm).
The Exclusivity of Multivalency in Dynamic Covalent Processes
作者:Jovica D. Badjić、Stuart J. Cantrill、Robert H. Grubbs、Erin N. Guidry、Raul Orenes、J. Fraser Stoddart
DOI:10.1002/anie.200453963
日期:2004.6.21
US8299276B2
申请人:——
公开号:US8299276B2
公开(公告)日:2012-10-30
Bifunctional [c2]Daisy-Chains and Their Incorporation into Mechanically Interlocked Polymers
作者:Erin N. Guidry、Jean Li、J. Fraser Stoddart、Robert H. Grubbs
DOI:10.1021/ja0725100
日期:2007.7.1
A strategy for the formation of mechanically interlocked polymers is presented. Ring-closing olefin metathesis has been shown to provide a very high yielding route to [c2]daisy-chains suitably functionalized to allow their one-step conversion to bisolefins which can be used as monomers in ADMET polymerizations to afford mechanically interlocked polymers. Metathesis, in two different guises is making a hitherto unreachable goal in synthesis a reality.