Issue in Honor of Prof. Alexander I. Konovalov ARKIVOC 2004 (xii) 38-46
Synthesis of in,out-isomeric phosphite and phosphate cryptands
Ingmar Bauer,a* Gulnur G. Sergeenko,b Il'yas S. Nizamov,b Gabriele Theumer,a Roland Fröhlichc, Alexander R. Burilov,b Vera I. Maslennikovad, and Wolf D. Habichera*
a Institute of Organic Chemistry, University of Technology Dresden, 01062 Dresden (Germany) b Arbuzov Institute of Organic and Physical Chemistry, RAS, Arbuzov str. 8, 420088 Kazan, Russia c Institute of Organic Chemistry, University Münster, Corrensstrasse 40, D-48149, Münster, Germany. d Moscow Pedagogical State University, Nesvizhsky per. 3, Moscow, 119021, Russia E-mail:
[email protected];
[email protected]
Dedicated to Professor Alexander I. Konovalov on his 70th birthday (received 29 Oct 04; accepted 08 Jan 05; published on the web 16 Jan 05)
Abstract The reaction of POCl3 with the trinuclear bisphenol 1 has been investigated. All three homeomorphic in,out-isomers of the phosphorus cryptand were isolated. Among them the out,out-isomer was the main macrobicyclic product obtained. The reaction of the previously described in,in-phosphite 2 with CuCl afforded an interesting complex containing two metal centers bridging the cavity of the cryptand together with a central chloride ion. This complex suggested the use of Cu(I) as a template for the formation of the formerly described in,outphosphite cryptands. With this method it is now possible to carry out the reaction in higher concentrated solution to isolate larger quantities of the phosphorus macrobicycles.
Keywords: Cryptands, phosphites, phosphates, in,out-isomers, macrocycles
Introduction
Phosphorus containing cryptands are interesting molecules with potential applications in various fields of chemistry. With trivalent phosphorus incorporated into a macrobicyclic skeleton, such structures can be potential ligands for the complexation of soft metals, a feature that makes them promising candidates for selective extraction of metal cations from aqueous solution or as catalysts in transition metal catalyzed reactions such as hydroformylation, Heck reaction, Suzuki coupling and others. Pentavalent phosphoryl compounds are interesting for complexation and separation of lanthanides and actinides. The macrocyclic framework can support the complexation and selectivity by either providing the appropriate size for a specific metal or
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