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
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
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 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.
