Bile Acid Derived Tropos Vaulted Binaphthylphosphites: Synthesis, Stereochemical Characterization and Complexation to Rhodium

作者：Jumde Varsha R; Iuliano Anna^*

来源：European Journal of Organic Chemistry, 2013, 2013(20): 4294-4302.

DOI：10.1002/ejoc.201300024

• Ligand design
• Rhodium
• Atropisomerism
• Configuration determination
• Circular dichroism

%26lt;title content-type=%26quot;main%26quot;%26gt;Abstract %26lt;br%26gt;Three different 2,2-binaphthylphosphites were synthesized, starting from suitable derivatives of cholic or deoxycholic acids and 1,1-dihydroxy-2,2-binaphthyl, and their stereochemical features were analyzed by CD and NMR spectroscopy. The spectroscopic data clearly demonstrate the capability of the cholestanic backbone to induce a M prevalent screw sense to the flexible binaphthyl moiety, giving rise to tropos ligands. The extent of the prevalence of the M sense of twist depends on the position at which the binaphthylphosphite moiety is linked on the bile acid skeleton. The three phosphites were mixed with [Rh(COD)(2)][BF4] and the resulting complexes were analyzed by variable temperature P-31 NMR spectroscopy, thereby obtaining information on their stereochemical characteristics, which reflect the different asymmetric induction capability of the ligands.

• 出版日期2013-7