Abstract
A series of chiral C
2 -symmetrical
macrocycles containing two α-amino acids and two biaryl
subunits have been designed and synthesized in moderate yields (36-53%).
The absolute configurations of biaryl motifs in these chiral macrocycles
were established by X-ray crystal structure analysis and CD measurements.
Key words
chiral macrocycle - biaryl -
C
2 -symmetrical - absolute configuration - X-ray analysis
References and Notes
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General Procedure
for the Syntheses of Chiral Macrocycles of 11a-c
To
a well-stirred solution of 10a -c in anhyd CH2 Cl2 was added
TFA. The resulting solution was stirred at r.t. for 2 h. The excess
TFA was removed under the reduced pressure. The residue was dissolved
in CH2 Cl2 and washed with sat. aq NaHCO3 three
times. The organic layers were dried over anhyd Na2 SO4 .
After filtration and concentration, the resulted residue was treated
with 5% AcOH (aq) in CH2 Cl2 at 40 ˚C
overnight. The reaction mixture was diluted with CH2 Cl2 ,
and washed with H2 O three times. The organic layers were
dried over anhyd Na2 SO4 . After filtration
and concentration under reduced pressure, the resulted crude products
were purified with flash column to afford macrocycles 11a -c in
36-53% yield.Analytical
Data of Chiral Macrocycle (
R
,
R
,
M
,
M
)-11a
[α]D
²³ -296.0
(c 1.0, CHCl3 ). ¹ H
NMR (400 MHz, CDCl3 ): J = 8.0,
1.2 Hz, 2 H), 7.53 (s, 2 H), 7.23-7.49 (m, 10 H), 7.12
(d, J = 7.6
Hz, 2 H), 7.07 (dd, J = 7.6,
1.2 Hz, 2 H), 3.64 (q, J = 6.8
Hz, 2 H), 3.38 (s, 6 H), 1.15 (d, J = 6.8 Hz,
6 H). ¹³ C NMR (100 MHz, CDCl3 ): δ = 172.6,
160.3, 142.2, 138.1, 138.0, 133.5, 132.9, 130.2, 129.7, 128.9, 128.7,
128.3, 128.1, 127.6, 63.1, 39.8, 21.8. ESI-HRMS: m/z calcd for C34 H33 N4 O2 [M + H+ ]:
529.2598; found: 529.2601 (-0.5 ppm, -0.3 mmu).
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Zhu JP.
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16 The X-ray crystallographic data of
compounds 11b and 11c were
deposited to the Cambridge Crystallographic Data Centre, CCDC-773495
and CCDC-773496, respectively.
