ORGANIC
LETTERS
2
007
Vol. 9, No. 26
641-5643
New Synthetic Path to
,2 -Bipyridine-5,5 -dicarbaldehyde and
Its Use in the [3 3] Cyclocondensation
5
2
′
′
+
with trans-1,2-Diaminocyclohexane
Jana Hoda cˇ ov a´ *,†,‡ and Milo sˇ Bud eˇ sˇ ´ı nsk y´ †
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech
Republic, FlemingoVo n a´ m. 2, 16610 Prague 6, Czech Republic, and Department of
Organic Chemistry, Institute of Chemical Technology, Technick a´ 5,
16628 Prague 6, Czech Republic
Received October 26, 2007
ABSTRACT
2 ′-Bipyridine-5,5′-dicarbaldehyde has been prepared in two steps by enamination of 5,5′-dimethyl-2,2′-bipyridine with Bredereck’s reagent,
,2
and subsequent oxidative cleavage of the enamine groups with sodium periodate. On condensation of this dialdehyde with enantiomerically
pure trans-1,2-diaminocyclohexane, the macrocyclic [3 3] hexa Schiff base has been obtained in excellent yield. Its reduction has given large
macrocyclic hexaamine having three bipyridine units incorporated into the macrocycle structure.
+
Recent discovery of the highly efficient [3+3] cyclocon-
densation of (1R,2R)-trans-1,2-diaminocyclohexane with
macrocycle structure that can be further used in construction
of more complex molecular and supramolecular systems.
Highly efficient synthesis of trianglimine 1 possessing three
bipyridyl units in the macrocycle has been one of our aims.
1
terephthaldehyde has initiated research in the field of
2
formation of novel chiral trianglimines. Our interest in this
area has focused on incorporation of suitable units into the
To synthesize the trianglimine 1, we needed 2,2′-bipyri-
dine-5,5′-dicarbaldehyde 2 as a starting material. Previously,
two synthetic strategies have been published to synthesize
†
Academy of Sciences of the Czech Republic.
Institute of Chemical Technology.
‡
(
1) (a) Gawronski, J.; Kolbon, H.; Kwit, M.; Katrusiak, A. J. Org. Chem.
000, 65, 5768-5773. (b) Chadim, M.; Bud eˇ sˇ ´ı nsk y´ , M.; Hoda cˇ ov a´ , J.;
Z a´ vada, J.; Junk, P. C. Tetrahedron: Asymmetry 2001, 12, 127-133.
2) (a) Kuhnert, N.; Strassnig, C.; Lopez-Periago, A. M. Tetrahedron:
2
. In the first one, starting 5,5′-dimethyl-2,2′-bipyridine has
2
been transformed by radical bromination to 5,5′-bis(bro-
momethyl)-2,2′-bipyridine, from which 2 has been synthe-
(
Asymmetry 2002, 13, 123-128. (b) Kuhnert, N.; Lopez-Periago, A. M.
Tetrahedron Lett. 2002, 43, 3329-3332. (c) Kwit, M.; Gawronski, J.
Tetrahedron: Asymmetry 2003, 14, 1303-1308. (d) Kuhnert, N.; Rossignolo,
G. M. Org. Biomol. Chem. 2003, 1, 1157-1170. (e) Ma, C.; Lo, A.;
Abdolmaleki, A.; MacLachlan, M. J. Org. Lett. 2004, 6, 3841-3844. (f)
Kwit, M.; Skowronek, P.; Kolbon, H.; Gawronski, J. Chirality 2005, 17,
S93-S100. (g) Gawronski, J.; Gawronska, K.; Grajewski, J.; Kwit, M.;
Plutecka, A.; Rychlewska, U. Chem. Eur. J. 2006, 12, 1807-1817.
3
sized by the Sommelet reaction. In the second approach,
5,5′-bis(hydroxymethyl)-2,2′-bipyridine has been selectively
(3) De Mendoza, J.; Mesa, E.; Rodriquez-Ubis, J. C.; Vazquez, P.;
Voegtle, F.; Windscheif, P. M.; Rissanen, K.; Lehn, J.-M.; Lilienbaum, D.;
Ziessel, R. Angew. Chem., Int. Ed. 1991, 30, 1331-1333.
1
0.1021/ol702612t CCC: $37.00
© 2007 American Chemical Society
Published on Web 11/21/2007