Abstract
Reaction of pentacyclo[5.4.0.02,6.03,10 .05,8 ]undecane-8-thione (7 ) with diazomethane (9a ) and 2-diazopropane (9b ) afforded the 1,3,4-thiadiazolines 12a and 12c , which subsequently were used as precursors of reactive thiocarbonyl ylides 13a ,b , respectively. Diphenyldiazomethane reacted rapidly with 7 to yield thiirane 14c as the final product. When decomposition of 12a or 12c was carried out in the presence of dipolarophiles, such as TCNE, DMAD or N -methylmaleinimide, new cage-functionalized heterocycles were obtained.
Key words
cage thioketones - diazo compounds - cycloaddition - spiro-heterocycles - thiocarbonyl
ylides
References
<A NAME="RC04103SS-1">1 </A>
Eaton PE.
Tetrahedron
1986,
42:
1549
2a </A>
Gerzon K.
Krumkalus EV.
Brindle RL.
Marshall FJ.
Root MA.
J. Med. Chem.
1963,
6:
760
2b </A>
Aldrich PE.
Hermann EC.
Meier WE.
Paulshock M.
Prichard WW.
Synder JA.
Watts JC.
J. Med. Chem.
1971,
14:
535
<A NAME="RC04103SS-3">3 </A>
Cookson RC.
Crundwell E.
Hudec J.
Chem. Ind. (London)
1958,
1003
4a </A>
Cookson RC.
Crundwell E.
Hill RR.
Hudec J.
J. Chem. Soc.
1964,
3062
4b </A>
Marchand AP. In
Advances in Theoretically Interesting Molecules
Vol. 1:
Thummel RP.
JAI;
Greenwich:
1989.
p.357-399
4c </A>
Mehta G.
Srikrishna A.
Veera Reddy A.
Nair MS.
Tetrahedron
1981,
37:
4543
5a </A>
Sasaki T.
Eguchi S.
Kiriyama T.
Hiroaki O.
Tetrahedron
1974,
30:
2707
5b </A>
Marchand AP.
Arney BE.
Dave PR.
Satyanarayana N.
J. Org. Chem.
1988,
53:
8644
5c </A>
Marchand AP.
Keith JM.
Alihodzic S.
Ganguly B.
Somers AW.
Hariprakasha HK.
Power TD.
Watson WH.
Bodige SG.
Struct. Chem.
2001,
12:
313
5d </A> For a review, see:
Marchand AP.
Kumar KA.
McKim AS.
Alihodzic S.
Chong H.-S.
Krishnudu K.
Takhi M.
Mlinaric-Majerski K.
Kragol G.
Sumanovac T.
Kem. Ind.
2001,
50:
129
6a </A>
Watson WH.
Marchand AP.
Dave PR.
Acta Crstallogr., Sect. C
1987,
43:
1569
6b </A>
Bott SG.
Marchand AP.
Kumar KA.
Vidyanand D.
Xing D.
Watson WH.
Kashyap RP.
Sachleben R.
J. Chem. Crystallogr.
1995,
25:
633
<A NAME="RC04103SS-7">7 </A>
Marchand AP.
Aldrichimica Acta
1995,
28:
95 ; and references cited therein
<A NAME="RC04103SS-8">8 </A>
Romański J.
Mlostoń G.
Synthesis
2002,
1355
<A NAME="RC04103SS-9">9 </A>
Eaton PE.
Cassar L.
Hudson RA.
Hwang DR.
J. Org. Chem.
1976,
42:
1445
<A NAME="RC04103SS-10">10 </A>
Greidanus JW.
Can. J. Chem.
1970,
48:
3530
11a </A>
Mlostoń G.
Romański J.
Linden A.
Heimgartner H.
Polish J. Chem.
1996,
70:
595 ; Chem. Abstr. 1996 , 125 , 86562
11b </A>
Mlostoń G.
Huisgen R.
Polborn K.
Tetrahedron
1999,
55:
11475
<A NAME="RC04103SS-12">12 </A>
Huisgen R.
Mlostoń G.
Polish J. Chem.
1999,
73:
635 ; Chem. Abstr. 1990 , 130 , 352041
13a </A>
Mlostoń G.
Heimgartner H. In The Chemistry of Heterocyclic Compounds, Synthetic Application of 1,3-Dipolar Cycloaddition
Chemistry Toward Heterocyclic and Natural Products
Vol. 59:
Padwa A.
Pearson W.
Wiley;
New York:
2002.
p.315-360
13b </A> Review:
Mlostoń G.
Heimgartner H.
Polish J. Chem.
2000,
74:
1503
<A NAME="RC04103SS-14">14 </A>
Huisgen R.
Mlostoń G.
Polborn K.
Sustmann R.
Chem. Eur. J.
2003,
9:
2256 ; and references cited therein
<A NAME="RC04103SS-15">15 </A>
Mlostoń G.
Huisgen R.
Giera H.
Tetrahedron
2002,
58:
4185
<A NAME="RC04103SS-16">16 </A>
Romański, J.; Mlostoń, G.; Szynkiewicz, S; Linden, A., manuscript in preparation.
<A NAME="RC04103SS-17">17 </A>
Huisgen R.
Li X.
Giera H.
Langhals E.
Helv. Chim Acta
2001,
84:
981
<A NAME="RC04103SS-18">18 </A>
Romański, J.; Mlostoń, G.; Szynkiewicz, S; Grabowski, S., manuscript in preparation.
19a </A>
Meerwein R.
Ber. Dtsch. Chem. Ges.
1942,
75:
1618
19b </A>
Staudinger H.
Ber. Dtsch. Chem. Ges.
1916,
49:
1915
<A NAME="RC04103SS-20">20 </A>
Staudinger H.
Anthes G.
Pfenninger F.
Ber. Dtsch. Chem. Ges.
1916,
49:
1939
<A NAME="RC04103SS-21">21 </A>
Huisgen R.
Penelle J.
Mlostoń G.
Buyle-Padias A.
Hall HK.
J. Am. Chem. Soc.
1992,
114:
266
