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Dialdehyde + DiamineЧPolymer or Macrocycle.

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source were as follows: bulk gas pressure 0.1 -0.2 Torr, source temperature 180°C.
emission current 1 mA, repeller voltage 0 V, electron energy 100 eV. The MIKE
spectra were recorded by using an accelerating potential of 8 KeV at a typical energy
resolution of 8 x lo3, and represent the average of at least 100 scans. CAD spectra
were taken by admitting He into the collision cell at such a pressure to reduce the
main beam intensity to 30% of its initial value.
Compu/utronal Delaib: Ab initio quantum-mechanicalcalculations were performed
by using a RISC/6000 version of the GAUSSIAN 92 program package [14]. The
standard internal 6-31G* [ISa], 6-311G** [15b], 6-311 G** [16], and 6-311G**
(2df) [16] basis sets were employed. Geometry optimizationswere performed in the
full space of the coordinates by analytical gradient-based techniques [17], in the
framework of the second-order Meller-Plesset perturbation theory [lS], with the
6-31G* basis set. The MP2 method was used with full (FU) electron correlation
(including inner-shell electrons). The geometries obtained (Fig. 1) in this way are
denoted by MP2(FU)/6-31G*. The corresponding vibrational frequencies were
computed for all of the species investigated, in order to characterize them as true
minima, transition structures, or higher order saddle points on the potential energy
hypersurface. The zero-point energy of the various species was accounted for in this
way. The GAUSSIAN-1 procedure, as outlined in ref. [13]. was employed to obtain
the total energies of the investigated species.
+
(S)-2contain two salicylaldehyde residues in a chiral binaphthyl
~ y s t e m . [ ~The
. ~ ] synthesis of 2,2'-dihydroxy-I ,l'-binaphthyl3,3'-dialdehyde (2) proceeds by 1,l'-coupling of the commercially available 3-hydroxy-2-naphthoic acid, acetylation of the phenolic OH groups, reduction of the acid chloride, and cleavage of
Enanthe protecting groups, in an overall yield of about 20 YO.[~I
tiomeric resolution takes place at the 2,2'-dihydroxy-I ,I1-binaphthyl-3,3'-dicarboxylic acid stage.[51
Received: June 15, 1993 [Z 6143 IE]
German version: Angew. Chem. 1994, 106, 104
[l] K. C. Smyth, T. W. Shannon, J. Chem. Phys. 1969, 51. 4633.
[2] J. H. Beynon, R. G. Cooks, Res. Dev. 1971, 22, 26.
[3] J. H. Homes, A. D. Osborne, In/. .
I
Mass Spectrum. Ion Phys. 1979, 32, 35.
[4] J. E. Szulejko, A. Mendez Amaya, R. P. Morgan, A. G. Brenton, J. H. Beynon,
Proc. R. Soc. London A 1980, 373, 1.
[5] B. A. Runpf, P. J. Derrick, Int. J. Mass. Spectrum. Ion Processes 1988,82, 239.
161 J. L. Holmes, Org. Mass Spectrum. 1985, 20, 169.
[7] B. Brehm. G. De Frenes, Adv. Mass Spectrum. 1979, 8, 138.
[S] F. Cacace. M. Attind, G. de Petris, M. Speranza. J. Am. Chem. Soc. 1990, 112,
1014.
191 F. Grandinetti. J. HruSik, D. Schroder, S. Karrass, H. Schwarz, J. A m . Chem.
Soc. 1992, 114. 2806.
[lo] G. de Petris. Org. Mass Spec/rom. 1990, 25, 83.
[ l l ] G. de Petris. Orz. Mass Spectrum. 1990, 25, 557.
[12] C. Meredith, R. A. D a y , H. F. Schaefer 111, J. Chem. P h w . 1990, 93, 1215.
[I31 J. A. Pople, M. Head-Gordon, D. J. Fox, K. Raghavachari, L. A. Curtis, J.
Cliem. P h w . 1989, 90, 5622.
[141 M. J. Frisch. G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B.
Foresman. B. G. Johnson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R.
Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L.
Martin. D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, J. A. Pople, Gaussian
92. Revision A, Gausslan, Inc., Pittsburgh, PA, 1992.
[IS] a) P. C. Hariharan, J. A. Pople, Chem. Phjs. L e f t . 1972. 66, 217; b) R. Krishnann, J. S. Binkley. R. Seeger, J. A. Pople, ihid. 1980, 72, 4244.
[16] M . J. Frisch. J. A. Pople, J. S. Binkley, Chem. Phys. Lett. 1984, X U , 3265.
[17] H. B. Schle_eel,J1 Comput. Chen?. 1982, 3 , 214.
[18] C. M d e r , M. S. Plesset, Phys. Rev. 1934, 46, 86.
The condensation of salicylaldehyde (1) with the difunctionalized amine 1,2-diaminoethane yields the known tetradentate
salen ligand. In contrast to the monofunctionalized aldehyde 1,
the binaphthyl derivatives 2 are difunctionalized, and should
therefore react with (R,R)-1,2-diamino-l ,2-diphenylethaner6,71
(3) to give polymeric Schiff bases. This supposition is confirmed
by the reaction of (R)-2with 3, but not by the reaction of (S)-2
with 3, in which two molecules of dialdehyde undergo condensation with two molecules of diamine to form the 24-membered
macrocycle 4. Compound 4 is a yellow solid that may be purified
by chromatography on silica gel.ISIAn m/z value of 1037 in the
mass spectrum confirms the above formulation. Obviously during the condensation of (R)-2 with 3, the ends of the growing
chain are so far apart from one another that the anticipated
polymer forms, whereas in the reaction of ( 9 - 2 with 3, the
24-membered ring closes.
H
Ph ti H P h
i l ;/
,c-c
+
-
\
2 tizN
4
NHZ
1-120
3
Dialdehyde + DiaminePolymer or Macrocycle?
Henri Brunner* and Hubert Schiessling
Dedicated to Projessor Otto J. Scherer
on the occasion o j his 60th birthday
Schiff bases derived from salicylaldehyde (1) and primary
amines are common chelating ligands in complex chemistry."]
Optically active salicylaldiminates have, for some time, also
been employed successfully in enantioselective catalysis (e.g. cyclopropanation).[21The optically active compounds (R)-2 and
4
[*] Prof. Dr. H. Brunner, Dipl.-Chem. H. Schiessling
Institut fur Anorganische Chemie der Universitat
D-93040 Regensburg (FRG)
Tekfax: Int. code + (941)943-4439
Angew. Chem. I n / . Ed. EngI. 1994. 33, N o . 1
8
A simple enantiomeric separation exploits the observation
that with the given optically active diamine 3, only the S enantiomer of aldehyde 2 gives rise to a macrocycle, whereas the R
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125
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enantiomer forms a polyimine. When the products of the reaction of (R)-2 and (S)-2 with 3 are subjected to column chromatography on silica gel, the macrocycle formed from the reaction of (S)-2 with 3 is eluted with dichloromethane/toluene as an
orange band, whilst the polyimine arising from (R)-2 is left as a
residue on the column. Stirring of 4 with hydrochloric acid
liberates (S)-2, which may then be isolated enantiomerically
pure.
The large-scale synthesis of racemic 2 is achieved from the
commercially available l,l’-binaphthyl-2,2’-di0l.~~~
This is first
methylated with NaH/dimethylsulfate, and then formylated ortho to the methoxy groups with BuLi/DMF/HCI, before the
methoxy groups are cleaved with boron trichloride. With the
procedure described, 2 may be obtained optically pure without
laborious recrystallization. This new enantiomeric separation of
2 is considerably less costly than the original synthetic route.f31
The new macrocycle 4 should be able to form complexes of
defined stereochemistry with up to four metal centers on both
sides of the molecule.
Experimental Procedure
4: Racemic 2 (4.39g. 12.8mmoI) and 3 (2.80g. 13.2mmol) were stirred together in
dichloromethane (100 mL) at room temperature for 24 h. Monitoring by thin-layer
chromatography (dichloromethane as eluent) showed complete consumption of 2.
The solvent was removed. and the residue chromatographed on silica in portions of
1 g (column 1 m x 3 cm, dichloromethane/toluene 9: 1. temperature - 18 T).
The
band containing the macrocycle 4 is distinguished by its orange color. Yield: 1.40 g
(1.35 mmol; 42% based on a singleenantiomer of2);yellow powder, turning brown
126
0 VCH VerIugsgesellsrhaft mbH. 0-69451 Wcitilreim. 1994
> 270 ‘C. Macrocycle 4 contains approximately 0.5 moles of dichloromethane.
which is in agreement with the ‘H NMR spectrum and elemental analysis. MS(FD,
CH,CI,): 1037 MH’: ‘H NMR (CDC13. 250 MHz, TMS): S = 12.62 (s. 4H), 8.42
-1635 cm-I.
(s. 4H). 7.34-6.72 (m. 40H). 4.96 (s. 4H): IR (KBr):
2: For the liberation of (9-2. the yellow powder 4 is dissolved in dichloromethane
(50mL) and stirred for 24 h with 5 N HCI (100mL). after which thedichloromethane
is distilled off. The dialdehyde (S)-2 is then filtered off and washed free of acid.
Purification is accomplished by column chromatography on silica/dichloromethane. with the isolation of 830 mg (2.42 mmol. 90%) (S)-2. [2]&, = - 250 (literature value: -248 [3]). (r = 0.3. CH,CI,).
After elution of 4. the polyimine can be washed from the column with acetone.
Liberation of aldehyde from the polyimine with 5 N HCI affords a mixture containing all of the (R)-2 and 50-60% of the (S)-2 initially present.
Received: August 10.1993 [Z6269IE]
German version: Angew. Chem. 1994,106,130
11)
E A. Cotton. G. Wilkinson. Inorgunir Chemistry. Verlag Chemie. Weinheim,
1982. p. 140. and references therein.
[2] 1.Aratdni. Pure Appl. Client. 1985. 57. 1839.
(31 H. Brunner, J. Goldbrunner, Cheni. Ber. 1989, 122. 2005.
(41 H. Brunner. K. Wutz. New J. Chon. 1992. 16.57.
[5] K. Weil. W. Kuhn. Helv. Cltiin. A r m 1944. 27, 1848.
[6] E. J. Corey, R. Imwinkelried. S. Pikul, Yi Bin Xiang. J. Am. C h i . SOC.1989.
I I I. 5493.
[7] K. Saigo. N. Kubota. S. Takebayashi. M.Hasegawa. Bull. Chem. Soc. Jpn. 1986.
59.931.
[8] Compared with similar imines. the macrocycle 4 has notably enhanced resistance towards hydrolysis, which makes possible its purification by column chromatography on silica.
191 L. F. Tietze, T. Eicher. Reuaktionen und Syiitlresen. Thieme, Stuttgart. 1981. p.
394.
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