Abstract
A simple, nearly quantitative method is demonstrated for the deprotection of tosylated
mixed azathiacrown ethers using sodium amalgam. Four macrocycles, containing differing
numbers of amino groups and ring sizes, were prepared using traditional cyclization
procedures and the described deprotection technique. Three of the macrocycles, [12]aneNS3 , [14]aneNS3 , and [15]aneN2 S3 , were reported previously, though either in low yields, only in protected form, or
using hazardous precursors, while the fourth, [18]aneN3 S3 , is a new ionophore.
Key words
supramolecular chemistry - crown compounds - macrocycles - ligands - reductions
References
<A NAME="RM04605SS-1">1 </A>
Comprehensive Supramolecular Chemistry
Vol. 1:
Gokel GW.
Atwood JL.
Davies JE.
MacNicol DD.
Vögtle F.
Pergamon;
Oxford:
1996.
2a </A>
Cooper SR.
Rawle SC.
Struct. Bonding (Berlin)
1990,
72:
1
2b </A>
Blake AJ.
Schröder M.
Adv. Inorg. Chem.
1990,
35:
1
<A NAME="RM04605SS-3">3 </A>
Bradshaw JS.
Krakowiak KE.
Izatt RM.
Aza-Crown Macrocycles , In Chemistry of Heterocyclic Compound s
Vol. 51:
Taylor EC.
Wiley;
New York:
1993.
<A NAME="RM04605SS-4">4 </A> For example, see:
Glenny MA.
Blake AJ.
Wilson C.
Schröder M.
J. Chem. Soc., Dalton Trans.
2003,
194 ; and references cited therein
<A NAME="RM04605SS-5">5 </A>
Tanaka M.
Nakamura M.
Ikeda T.
Ikeda K.
Ando H.
Shibutani Y.
Yajima S.
Kimura K.
J. Org. Chem.
2001,
66:
7008
<A NAME="RM04605SS-6">6 </A>
Hart SM.
Boeyens JAC.
Michael JP.
Hancock RD.
J. Chem. Soc., Dalton Trans.
1983,
1601
<A NAME="RM04605SS-7">7 </A>
Chak B.
McAuley A.
Whitcombe TW.
Inorg. Chim. Acta
1996,
246:
349
<A NAME="RM04605SS-8">8 </A>
Blake AJ.
Lippolis V.
Schröder M.
Acta Crystallogr., Sect. E: Struct. Rep. Online
2004,
60:
o901
<A NAME="RM04605SS-9">9 </A>
McAuley A.
Subramanian S.
Inorg. Chem.
1990,
29:
2830
<A NAME="RM04605SS-10">10 </A>
Sibert JW.
Forshee PB.
Lynch V.
Inorg. Chem.
2005,
44:
8602
<A NAME="RM04605SS-11">11 </A>
Trost BM.
Arndt HC.
Strege PE.
Verhoeven TR.
Tetrahedron Lett.
1976,
39:
3477
<A NAME="RM04605SS-12">12 </A>
Vriesema BK.
Butler J.
Kellogg RM.
J. Org. Chem.
1984,
49:
110
<A NAME="RM04605SS-13">13 </A>
Sessler JL.
Sibert JW.
Hugdahl JD.
Lynch V.
Inorg. Chem.
1989,
28:
1417
<A NAME="RM04605SS-14">14 </A>
In our procedure, the reaction was performed without external heat under an argon
atmosphere with the reaction apparatus placed in an oil bath. After initiating the
reaction by addition of a small amount of mercury to the sodium metal, the remaining
mercury was immediately and quickly added (approx. 10-15 s total addition time) via
an addition funnel with rapid stirring at room temperature. The amounts of reagents
and reaction workup were as reported in ref. 15.
<A NAME="RM04605SS-15">15 </A>
Fieser LF.
Fieser M.
Reagents for Organic Synthesis
Wiley;
New York:
1967.
p.1030
<A NAME="RM04605SS-16">16 </A>
van de Water LA.
Buijs W.
Driessen WL.
Reedijk J.
New J. Chem.
2001,
25:
243
<A NAME="RM04605SS-17">17 </A>
Westerby BC.
Juntunen KL.
Leggett GH.
Pett VB.
Koenigbauer MJ.
Purgett MD.
Taschner MJ.
Ochrymowycz LA.
Rorabacher DB.
Inorg. Chem.
1991,
30:
2109
<A NAME="RM04605SS-18">18 </A>
Atkins TJ.
Richman JE.
Oettle WF.
Org. Synth.
1978,
58:
86
