Conformational Control in Metallofoldamers: Design, Synthesis and Structural Properties

2009 ◽  
Vol 2009 (33) ◽  
pp. 5699-5710 ◽  
Author(s):  
Galia Maayan
2020 ◽  
Author(s):  
Takuya Murai ◽  
Wenjie Lu ◽  
Toshifumi Kuribayashi ◽  
Kazuhiro Morisaki ◽  
Yoshihiro Ueda ◽  
...  

Novel well-defined <i>D</i><sub>2</sub>-symmetric dirhodium(II) carboxylate complexes that bear axially chiral binaphthothiophene delta-amino acid derivatives have been developed. Conformational control was achieved through chalcogen-bonding interactions between sulfur and oxygen atoms in each ligand, providing well-defined and uniform asymmetric environments around the catalytically active Rh(II) centers. These structural properties render such complexes excellent catalysts for the inside-type asymmetric intramolecular C–H insertion into alpha-aryl-alpha-diazoacetates to yield a variety of <i>cis</i>- alpha, beta-diaryl gamma-lactones, as well as the corresponding <i>trans</i>-isomers through epimerization, in high diastereo- and enantioselectivities. Short total syntheses of the naturally occurring gamma-lactones cinnamomumolide, cinncassin A<sub>7</sub>, and cinnamomulactone were also accomplished using this conformationally controlled catalyst.<br><br>


2000 ◽  
Vol 33 (17) ◽  
pp. 6423-6438 ◽  
Author(s):  
Mikael Trollsås ◽  
Björn Atthof ◽  
Andreas Würsch ◽  
James L. Hedrick ◽  
John A. Pople ◽  
...  

1994 ◽  
Vol 7 (8) ◽  
pp. 1041-1052 ◽  
Author(s):  
Violetta V. Chemeris ◽  
Dmitry A. Dolgikh ◽  
Alexey N. Fedorov ◽  
Alexey V. Finkelstein ◽  
Michail P. Kirpichnikov ◽  
...  

2020 ◽  
Author(s):  
Takuya Murai ◽  
Wenjie Lu ◽  
Toshifumi Kuribayashi ◽  
Kazuhiro Morisaki ◽  
Yoshihiro Ueda ◽  
...  

Novel well-defined <i>D</i><sub>2</sub>-symmetric dirhodium(II) carboxylate complexes that bear axially chiral binaphthothiophene delta-amino acid derivatives have been developed. Conformational control was achieved through chalcogen-bonding interactions between sulfur and oxygen atoms in each ligand, providing well-defined and uniform asymmetric environments around the catalytically active Rh(II) centers. These structural properties render such complexes excellent catalysts for the inside-type asymmetric intramolecular C–H insertion into alpha-aryl-alpha-diazoacetates to yield a variety of <i>cis</i>- alpha, beta-diaryl gamma-lactones, as well as the corresponding <i>trans</i>-isomers through epimerization, in high diastereo- and enantioselectivities. Short total syntheses of the naturally occurring gamma-lactones cinnamomumolide, cinncassin A<sub>7</sub>, and cinnamomulactone were also accomplished using this conformationally controlled catalyst.<br><br>


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