TY - JOUR
T1 - Highly active ruthenium metathesis catalysts enabling ring-opening metathesis polymerization of cyclopentadiene at low temperatures
AU - Song, Kitaek
AU - Kim, Kunsoon
AU - Hong, Daeun
AU - Kim, Jungwon
AU - Heo, Chae Eun
AU - Kim, Hugh I.
AU - Hong, Soon Hyeok
N1 - Funding Information:
We thank S. H. Yang of Professor T. L. Choi’s group, and J. Y. Kim and J. W. Kim of Professor K. T. Kim’s group for helpful discussions. This work was supported by the National Research Foundation of Korea (NRF-2014R1A5A1011165, Center for New Direction in Organic Synthesis; NRF-2015M3D3A1A01065480; NRF-2015H1A2A1033766, Global PhD Fellowship Program).
Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - Development of versatile ruthenium olefin-metathesis catalysts with high activity, stability, and selectivity is a continuous challenge. Here we report highly controllable ruthenium catalysts using readily accessible and versatile N-vinylsulfonamides as carbene precursors. Catalyst initiation rates were controlled in a straightforward manner, from latent to fast initiating, through the facile modulation of the N-vinylsulfonamide ligands. Trifluoromethanesulfonamide-based catalysts initiated ultrarapidly even at temperatures as low as −60 °C and continuously propagated rapidly, enabling the enthalpically and entropically less-favored ring-opening metathesis polymerizations of low-strained functionalized cyclopentene derivatives, some of which are not accessible with previous olefin-metathesis catalysts. To our surprise, the developed catalysts facilitated the polymerization of cyclopentadiene (CPD), a feedstock that is easily and commonly obtainable through the steam cracking of naphtha, which has, to the best of our knowledge, not been previously achieved due to its low ring strain and facile dimerization even at low temperatures (below 0 °C).
AB - Development of versatile ruthenium olefin-metathesis catalysts with high activity, stability, and selectivity is a continuous challenge. Here we report highly controllable ruthenium catalysts using readily accessible and versatile N-vinylsulfonamides as carbene precursors. Catalyst initiation rates were controlled in a straightforward manner, from latent to fast initiating, through the facile modulation of the N-vinylsulfonamide ligands. Trifluoromethanesulfonamide-based catalysts initiated ultrarapidly even at temperatures as low as −60 °C and continuously propagated rapidly, enabling the enthalpically and entropically less-favored ring-opening metathesis polymerizations of low-strained functionalized cyclopentene derivatives, some of which are not accessible with previous olefin-metathesis catalysts. To our surprise, the developed catalysts facilitated the polymerization of cyclopentadiene (CPD), a feedstock that is easily and commonly obtainable through the steam cracking of naphtha, which has, to the best of our knowledge, not been previously achieved due to its low ring strain and facile dimerization even at low temperatures (below 0 °C).
UR - http://www.scopus.com/inward/record.url?scp=85071604718&partnerID=8YFLogxK
U2 - 10.1038/s41467-019-11806-5
DO - 10.1038/s41467-019-11806-5
M3 - Article
C2 - 31455772
AN - SCOPUS:85071604718
SN - 2041-1723
VL - 10
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 3860
ER -