ADMET Polymerization

Abstract

Acyclic diene metathesis (ADMET) polymerization is a synthetic strategy used to prepare polyolefins decorated with precisely spaced functional groups. Offered here is a survey of monomer design and synthesis, expert advice on α,ω‐diene monomer synthesis and purification, and a guide to selecting the optimal catalyst. In light of the advances in olefin metathesis catalysts and the library of ADMET polymers prepared, a discussion of what has been learned from these carefully prepared precision polymers is presented.

Synthesis of platinum-containing oligomers utilizing ADMET chemistry and polycondensation of a bisimide with α,ω-dibromoalkanes: examination of triplet–triplet annihilation upconversion

“…In the present study, we designed a novel Pt complex diene monomer bearing a symmetrical Pt center that undergoes acyclic diene metathesis (ADMET) oligomerization. [16][17][18][19][20] We also examined the polycondensation of a novel bisimide monomer bearing a symmetrical Pt center with α,ω-dibromoalkanes. [21][22][23][24][25] We examined the photoluminescence, oxygen sensing and sensitizing ability of TTA-UC of the formed oligomers.…”

cis-Selective Acyclic Diene Metathesis Polymerization of α,ω-Dienes

“…Polymerizations based on olefin metathesis, such as acyclic diene metathesis (ADMET) , and ROMP, represent a promising and versatile strategy to access a diverse pool of stereodefined polyalkenamers because of the robustness, functional-group tolerance, and structural diversity of metathesis catalysts. , Specifically designed W or Mo alkylidenes were found to overcome the thermodynamic preference of ROMP and to deliver high cis selectivity mostly with nonpolar monomers via kinetic control. , The recent development of Z -selective − and stereoretentive − Ru catalysts has allowed the expansion of the scope of cis -selective ROMP processes. − Interestingly, while ADMET is a powerful tool for the precise synthesis of polymers, , control over the stereochemistry of the repeating alkenes has long escaped this versatile polymerization.…”

“…ADMET typically delivers polymers with a predominance of trans alkenes with Grubbs and Hoveyda–Grubbs dichloro Ru catalysts (Scheme a). , We recently leveraged the exquisite stereoretention afforded by dithiolate Ru catalysts to produce a variety of all- cis polyalkenamers using cis , cis -diene monomers (Scheme b) . However, this method required the synthesis of monomers with preinstalled cis , cis stereochemistry and utilized air-sensitive Ru carbenes …”

“…Monomers containing a spectator cis-olefin have been used to circumvent this issue, 8−10 but undesired isomerization can erode the stereochemistry of the macromolecules. 11,12 Polymerizations based on olefin metathesis, such as acyclic diene metathesis (ADMET) 13,14 and ROMP, 15 represent a promising and versatile strategy to access a diverse pool of stereodefined polyalkenamers because of the robustness, functional-group tolerance, and structural diversity of metathesis catalysts. 16,17 Specifically designed W or Mo alkylidenes were found to overcome the thermodynamic preference of ROMP and to deliver high cis selectivity mostly with nonpolar monomers via kinetic control.…”

cis-Selective Acyclic Diene Metathesis Polymerization of α, ω-Dienes

“…Monomers containing a spectator cis olefin have been used to circumvent this issue, [8][9][10] but undesired isomerization can erode the stereochemistry of the macromolecules. 11,12 Polymerizations based on olefin metathesis such as acyclic diene metathesis (ADMET) 13,14 and ROMP 15 represent a promising and versatile strategy to access a diverse pool of stereodefined polyalkenamers because of the robustness, functionalgroup tolerance, and structural diversity of metathesis catalysts. Specifically designed W or Mo alkylidenes were found to overcome the thermodynamical preference of ROMP and to deliver high cis-selectivity mostly with non-polar monomers via kinetic control.…”