Hofmann M, Höhn C, Heinemann FW, Zenneck U (2009)
Publication Status: Published
Publication Type: Journal article
Publication year: 2009
Book Volume: 15
Pages Range: 5998-6007
Journal Issue: 24
An effective cyclic addition reaction of diastereomeric (R*)diphenyltin-3,5-di(tert-butyl)-1,2,4-triphosphole derivatives 6 a-c (R* = (-)-cis-myrtanyl (a), (-)-trans-myrtanyl (b), m-(2-bornyl-2-ene)phenyl (c) with two equivalents of tert-butylphosphaalkyne 1 leads to 1:1 mixtures of diastereomeric stannylated pentaphosphadeltacyclene derivatives 7 a-c with seven stereogenic centers in the cage unit. The (-)-cis-myrtanyl derivative 7 a could be separated into its diastereomers; destannylation of diastereomer 7 a(RR) led to the P-H cage 8 as a pure enantiomer. Circular dichroism (CD) spectroscopy of the pure diastereomer 7 a(RR) and the enantiomer 8 give evidence for identical stereoisomers of the P(5)-deltacyclene cage units and prove a strong dominance of the chiral cages over the chiral auxiliary groups with respect to their chiroptical properties. Absolute X-ray structure investigations of the majority of the compounds presented in the paper reveal the details of the stereochemistry of the asymmetric P-C cage units. In this paper we demonstrated for the first time a general preparative route to stereochemically fully defined asymmetric P-C cage compounds by separation of diastereomers and replacement of the chiral auxiliary group.
APA:
Hofmann, M., Höhn, C., Heinemann, F.W., & Zenneck, U. (2009). Cage chirality of P-C cage compounds: highly diastereoselective formation of diastereomeric P5-deltacyclenes, separation of diastereomers, and removal of the chiral auxiliary. Chemistry - A European Journal, 15(24), 5998-6007. https://doi.org/10.1002/chem.200801721
MLA:
Hofmann, Martin, et al. "Cage chirality of P-C cage compounds: highly diastereoselective formation of diastereomeric P5-deltacyclenes, separation of diastereomers, and removal of the chiral auxiliary." Chemistry - A European Journal 15.24 (2009): 5998-6007.
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