It remains a challenging task to achieve ring-opening(co)polymerization(ROP)of macrolactones.Hence,we synthesized a series of Al-based catalysts and systemically investigated the effect of N-containing substituent on ...It remains a challenging task to achieve ring-opening(co)polymerization(ROP)of macrolactones.Hence,we synthesized a series of Al-based catalysts and systemically investigated the effect of N-containing substituent on the sidearms on ROP of macrolactones.Al3 possessing Nmethyl group could effectively achieve controlled ROP of pentadecalactone(PDL)and macro(di)lactone ethylene brassylate(EB)in combination with BnOH,furnishing polyethylene-like PPDL and PEB with M_(W)up to 90.3 and 321 kg/mol,respectively.Random copolymerization of PDL and small-ring lactonesε-caprolactone(e-CL)andδ-valerolactone(δ-VL)could prepare random copolyesters with tailored T_(m)in the range of 57-94℃by controlling the ratios of PDL and e-CL,6-VL.More importantly,well-defined block copolyesters could be obtained by sequential adding PDL andε-CL,δ-VL,which have been proved by GPC-MALLS,DSC and^(13)C-NMR.展开更多
A novel macrolactonization method was developed using a chiral β-lactam as the template. This novel method features that the macrocyclization is simultaneously achieved while a TBS protected hydroxy group is deprotec...A novel macrolactonization method was developed using a chiral β-lactam as the template. This novel method features that the macrocyclization is simultaneously achieved while a TBS protected hydroxy group is deprotected.展开更多
A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were syn...A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.展开更多
Macrolactones play a critical role in pharmaceuticals and agrochemicals.Numerous efforts have been devoted to developing synthetic methods for them.We highlighted a recent progress for building macrocycles(≥12-member...Macrolactones play a critical role in pharmaceuticals and agrochemicals.Numerous efforts have been devoted to developing synthetic methods for them.We highlighted a recent progress for building macrocycles(≥12-membered)via bench-stable vinyl ester(VE)intermediates,which have been underdeveloped for half century.展开更多
基金the National Natural Science Foundation of China(Nos.22225104,22071077,21871107 and 21975102)China Postdoctoral Science Foundation(Nos.2022TQ0115 and 2022M711297)。
文摘It remains a challenging task to achieve ring-opening(co)polymerization(ROP)of macrolactones.Hence,we synthesized a series of Al-based catalysts and systemically investigated the effect of N-containing substituent on the sidearms on ROP of macrolactones.Al3 possessing Nmethyl group could effectively achieve controlled ROP of pentadecalactone(PDL)and macro(di)lactone ethylene brassylate(EB)in combination with BnOH,furnishing polyethylene-like PPDL and PEB with M_(W)up to 90.3 and 321 kg/mol,respectively.Random copolymerization of PDL and small-ring lactonesε-caprolactone(e-CL)andδ-valerolactone(δ-VL)could prepare random copolyesters with tailored T_(m)in the range of 57-94℃by controlling the ratios of PDL and e-CL,6-VL.More importantly,well-defined block copolyesters could be obtained by sequential adding PDL andε-CL,δ-VL,which have been proved by GPC-MALLS,DSC and^(13)C-NMR.
基金This work is supported by the National Natural Science Foundation of China (grant No: 20372056)a Research Fund from the Royal Society of Chemistry. UK.
文摘A novel macrolactonization method was developed using a chiral β-lactam as the template. This novel method features that the macrocyclization is simultaneously achieved while a TBS protected hydroxy group is deprotected.
基金Financial support from the National Natural Science Foundation of China(Nos.21971201,22171220)the Fundamental Research Funds of the Central Universities(No.xtr072022003)。
文摘A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.
基金the financial support from the Drug Innovation Major Project(No.2018ZX09711001-005)the Program of Shanghai Academic Research Leader(No.20XD1404700)+1 种基金the Key Research Program of Frontier Sciences(No.QYZDY-SSWSLH026)the Strategic Priority Research Program(No.XDB20000000)of the Chinese Academy of Sciences.
文摘Macrolactones play a critical role in pharmaceuticals and agrochemicals.Numerous efforts have been devoted to developing synthetic methods for them.We highlighted a recent progress for building macrocycles(≥12-membered)via bench-stable vinyl ester(VE)intermediates,which have been underdeveloped for half century.
