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DOI: 10.1055/s-0030-1258582
Asymmetric Synthesis and Structural Elucidation of C 2-Symmetrical Optically Active Macrocycles Consisting of Two Biaryl and Two α-Amino Acid Moieties
Publication History
Publication Date:
23 September 2010 (online)
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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
- Supporting Information for this article is available online:
- Supporting Information
- 1
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References and Notes
General Procedure
for the Syntheses of Chiral Macrocycles of 11a-c
To
a well-stirred solution of 10a-c in anhyd CH2Cl2 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 CH2Cl2 and washed with sat. aq NaHCO3 three
times. The organic layers were dried over anhyd Na2SO4.
After filtration and concentration, the resulted residue was treated
with 5% AcOH (aq) in CH2Cl2 at 40 ˚C
overnight. The reaction mixture was diluted with CH2Cl2,
and washed with H2O three times. The organic layers were
dried over anhyd Na2SO4. 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). ¹H
NMR (400 MHz, CDCl3):
δ = 7.63
(dd, 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). ¹³C 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 C34H33N4O2 [M + H+]:
529.2598; found: 529.2601 (-0.5 ppm, -0.3 mmu).
The X-ray crystallographic data of compounds 11b and 11c were deposited to the Cambridge Crystallographic Data Centre, CCDC-773495 and CCDC-773496, respectively.