Stereoselective P-5-Deltacyclene Alkylation, an Efficient Route to New Asymmetric P-C-Cage Compounds

Beitrag in einer Fachzeitschrift


Details zur Publikation

Autor(en): Keller I, Höhn C, Rohwer L, Heinemann F, Zenneck U
Zeitschrift: Zeitschrift für Anorganische und Allgemeine Chemie
Verlag: WILEY-V C H VERLAG GMBH
Jahr der Veröffentlichung: 2017
Band: 643
Heftnummer: 14
Seitenbereich: 922-931
ISSN: 0044-2313


Abstract

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.


FAU-Autoren / FAU-Herausgeber

Heinemann, Frank Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Höhn, Christine
Naturwissenschaftliche Fakultät
Keller, Irene
Naturwissenschaftliche Fakultät
Rohwer, Lars Dr.
Graduiertenzentrum der FAU
Zenneck, Ulrich Prof. Dr.
Naturwissenschaftliche Fakultät


Zitierweisen

APA:
Keller, I., Höhn, C., Rohwer, L., Heinemann, F., & 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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Zuletzt aktualisiert 2018-17-07 um 12:08