Keller I, Höhn C, Rohwer L, Heinemann FW, Zenneck U (2017)
Publication Status: Published
Publication Type: Journal article
Publication year: 2017
Publisher: WILEY-V C H VERLAG GMBH
Book Volume: 643
Pages Range: 922-931
Journal Issue: 14
Tetra-tert-butyl-P-5-deltacyclene 5 represents one of only two asymmetric P-C cage compounds, which are available in highly enantiomerically enriched versions. This paper reports about stereoselective substitution reactions of 5 to develop the chemistry of optically active P-C cages further. Electrophilic substitution of the only secondary phosphorus atom P1 of the cage with methyl and benzyl groups was achieved with 92% and >99% de, but the yields of the reactions are limited due to competing processes. The uncatalyzed hydrophosphination reaction of a monosubstituted allene and two alpha,beta-unsaturated carbonyl compounds with 5 proved to be the method of choice. cis-Butanone-P-5-deltacyclene 12 is formed in 92% yield and with >99% de and cis-pentanone-P-5-deltacyclene 13a is accessible with >99% de for P1 and 92% de for the attached carbon atom at the same time. Besides stereoselectivity, the hydrophosphination reaction of 5 performs with a good regioselectivity. The chiral cage 5 controls the stereoselectivity of its reactions for the cage elements as well as for the alpha position of a substituent.
APA:
Keller, I., Höhn, C., Rohwer, L., Heinemann, F.W., & Zenneck, U. (2017). Stereoselective P-5-Deltacyclene Alkylation, an Efficient Route to New Asymmetric P-C-Cage Compounds. Zeitschrift für Anorganische und Allgemeine Chemie, 643(14), 922-931. https://dx.doi.org/10.1002/zaac.201700132
MLA:
Keller, Irene, et al. "Stereoselective P-5-Deltacyclene Alkylation, an Efficient Route to New Asymmetric P-C-Cage Compounds." Zeitschrift für Anorganische und Allgemeine Chemie 643.14 (2017): 922-931.
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