A Remarkably Efficient and Direct Route for the Synthesis of Binucleating 1,4,7-Triazacyclononane Ligands

Abstract

An extremely efficient and direct route towards a range of binucleating analogues of 1,4,7-triazacyclononane 5a-f, has been developed. In all cases the reactions of benzylic and aliphatic diamines with ditosylate ester 3 proceed to give the target binucleating ligands almost exclusively and in excellent yield.

Key words

macrocycles - azamacrocycles - binucleating ligands - polyazacycloalkanes - 1,4,7-triazacyclononane

References

• 2 Wainwright KP. Coord. Chem. Rev.  1997,  166:  35 
• 3a Sessler JL. Sibert JW. Lynch L. Markert JT. Wooten CL. Inorg. Chem.  1993,  32:  621 
• 3b Brudenell SJ. Spiccia L. Bond AM. Fallon GD. Hockless DCR. Lazarev G. Mahon PJ. Tiekink ERT. Inorg. Chem.  2000,  39:  881 
• 4 Hage R. Iburg JE. Kerschner J. Koek JH. Lempers ELM. Martens RJ. Racherla US. Russell SW. Swarthoff T. van Vliet MRP. Warnaar JB. van der Wolf L. Krijnen B. Nature  1994,  369:  637 
• See for example
• 5a De Vos D. Bein T. Chem. Commun.  1996,  917 
• 5b Zondervan C. Hage R. Feringa BL. Chem. Commun.   1997,  419 
• 5c De Vos DE. Sels BF. Reynaers M. Subba Rao YV. Jacobs PA. Tetrahedron Lett.  1998,  3221 
• 5d Barton DHR. Li W. Smith JA. Tetrahedron Lett.  1998,  39:  7055 
• 5e Shul’pin GB. Süss-Fink G. Lindsay Smith JR. Tetrahedron  1999,  55:  5345 
• 6a Young MJ. Chin J. J. Am. Chem. Soc.  1995,  117:  10577 
• 6b Hegg EL. Burstyn JN. Inorg. Chem.  1996,  35:  7474 
• 6c McCue KP. Voss DA. Marks C. Morrow JR. J. Chem. Soc., Dalton Trans.  1998,  2961 
• 7a De Vos DE. Meinershagen JL. Bein T. Angew. Chem. Int. Ed. Engl.  1996,  35:  2211 
• 7b Gilbert BC. Kamp NWJ. Lindsay Smith JR. Oakes J. J. Chem. Soc., Perkin Trans 2.  1997,  2161 
• 7c De Vos DE. de Wilderman S. Sels BF. Grobert PJ. Jacobs PA. Angew. Chem. Int. Ed.  1999,  38:  980 
• 8a Weisman GR. Vachon DJ. Johnson VB. Gronbeck DA. J. Chem. Soc., Chem. Commun.  1987,  887 
• 8b Sessler JL. Sibert JW. Lynch V. Inorg. Chem.  1990,  29:  4143 
• 8c Blake AJ. Danks JP. Li W.-S. Lippolis V. Schröder M. J. Chem. Soc., Dalton Trans.  2000,  3034 
• 11 Sessler JL. Sibert JW. Burrell AK. Lynch V. Markert JT. Wooten CL. Inorg. Chem.  1993,  32:  4277 

1

Present address: Associated Octel, Oil Sites Road, Ellesmere Port, Merseyside, U.K.

9

Pulacchini, S.; Watkinson, M. Eur. J. Org. Chem. accepted for publication.

10

Wieghardt K., Tolksdorf I., Herrmann W.; Inorg. Chem.; 1985, 24: 1230-1235; the original report of these compounds provides no experimental data and indicates that the compounds contain impurities as judged by ¹³C NMR.