Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally ri...Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.展开更多
The selectivities, including peri-, regio-, and diastereoselectivities, in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory （DFT） calcu...The selectivities, including peri-, regio-, and diastereoselectivities, in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory （DFT） calculation. The results indicate that vicinal diimines prefer stepwise [2＋2] cycloaddition rather than [2＋4] cycloaddition to generate cis-4-imino-β-lactams. The diimines attack the less sterically hindered exo-side of ketenes to generate zwitterionic intermediates, which directly undergo a conrota- tory ring closure to produce cis-4-imino-β-lactams whatever diimines with less or more bulky N-substituents. For unsymmetric vicinal ketoaldehyde-derived diimines, their ketimines attack the exo-side of ketenes and undergo a conrotatory ring closure to produce cis-4-aldimino-β-lactams due to less steric effect. The current theoretical studies provide very important information for in-depth understanding of the selective formation of mono-cis-β-lactams from vicinal diimines and ketenes.展开更多
基金supported by the National Natural Science Foundation of China (21403022,21572226)the Natural Science Foundation of Liaoning Province of China (2015020194)~~
文摘Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.
文摘The selectivities, including peri-, regio-, and diastereoselectivities, in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory （DFT） calculation. The results indicate that vicinal diimines prefer stepwise [2＋2] cycloaddition rather than [2＋4] cycloaddition to generate cis-4-imino-β-lactams. The diimines attack the less sterically hindered exo-side of ketenes to generate zwitterionic intermediates, which directly undergo a conrota- tory ring closure to produce cis-4-imino-β-lactams whatever diimines with less or more bulky N-substituents. For unsymmetric vicinal ketoaldehyde-derived diimines, their ketimines attack the exo-side of ketenes and undergo a conrotatory ring closure to produce cis-4-aldimino-β-lactams due to less steric effect. The current theoretical studies provide very important information for in-depth understanding of the selective formation of mono-cis-β-lactams from vicinal diimines and ketenes.
