Homochiral Supramolecular M2L4 Cages
FULL PAPER
tion. The solution was extracted three times with ethyl acetate, and the
combined organic phases were dried over Na2SO4. Removing the solvent
under reduced pressure led to the desired product in quantitative yield.
The analytical data are in accordance with the published ones.[14]
Synthesis of (P)-, (M)-, and (rac)-2,2’-di(methoxymethoxy)-3,3’-bis(3-
ethyndiyl-pyridyl)-1,1’-binapththyl (1): (P)-, (M)-, or (rac)-3,3’-diiodo-
2,2’-di(methoxymethoxy)-1,1’-binaphthyl (150 mg, 0.24 mmol), 3-ethynyl-
pyridine (71 mg, 0.5 mmol), [Pd2ACHTNUGTRENUNG(dba)3]·CHCl3 (11 mg, 9.6 mmol), 1,1’-
bis(diphenylphosphino)ferrocene (dppf; 10.6 mg, 19.2 mmol), and CuI
(8 mg, 38.3 mmol) were dissolved in dry triethyl amine (11 mL) and dry
THF (4 mL) and stirred at 458C for 66 h. The reaction was quenched
with saturated aqueous EDTA solution (30 mL). The resulting solution
was extracted five times with dichloromethane, and the combined organic
phases were dried over Na2SO4. The solvent was removed under reduced
pressure, and the crude product was purified by column chromatography
on silica-gel with a mixture of cyclohexane/ethyl acetate/triethyl amine
4:3:1 as eluent (Rf =0.36) to get the product as a yellow, pasty oil in 97%
yield. 1H NMR (400.1 MHz, CDCl3, 293 K): d=8.80 (dd, 4JH17,H14 =2.1,
5JH17,H15 =0.9 Hz, 2H, H17), 8.55 (dd, 3JH16,H15 =4.9 Hz, 4JH16,H14 =1.7 Hz,
5
2H, H16), 8.26 (s, 2H, H-4), 7.87 (ddd, 3JH5,H6 =8.5, 4JH5,H7 =1.2, JH5,H8
=
Figure 5. Supramolecular structures of [Pd2{(P)-1}4]ACHTNUGTRNEGNU(BF4)4 determined by
0.7 Hz, 2H, H5), 7.83 (ddd, 3JH14,H15 =8.0, 4JH14,H17 =2.1, 4JH14,H16 =1.8 Hz,
XRD analysis (color code: grey carbon; blue nitrogen; red oxygen; and
petrol palladium; solvent molecules, anions, and hydrogen atoms are
omitted for clarity).
2H, H14), 7.45 (ddd, 3JH7,H8 =8.2, 3JH7,H6 =6.9, 4JH7,H5 =1.2 Hz, 2H, H7),
7.32 (ddd, 3JH6,H5 =8.5, 3JH6,H7 =6.9, 4JH6,H8 =1.4 Hz, 2H, H6), 7.29 (ddd,
3
3J15,H14 =8.0, 3JH15,H16 =4.9, 5JH15,H17 =0.9 Hz, 2H, H15), 7.24 (ddd, JH8,H7
=
8.2, 4JH8,H6 =1.4, 5JH8,H5 =0.7 Hz, 2H, H8), 5.14 (d, 2JH9,H9a =À6.2 Hz, 2H,
H-9), 4.94 (d, 2JH9a,H9 =À6.2 Hz, 2H, H-9a), 2.54 ppm (s, 6H, H-
10);13C NMR (100.4 MHz, CDCl3, 293 K): d=153.0 (C2), 152.1 (C17),
148.7 (C16), 138.4 (C14), 134.6 (C4), 133.9 (C4a), 130.2 (C8a), 127.7
(C5), 127.6 (C-6); 126.5 (C8), 125.9 (C1), 125.7 (C7), 123.1 (C15), 120.4
(C13), 116.6 (C3), 99.0 (C9), 90.1 (C12), 89.7 (C11), 56.1 (C10); MS (ESI,
10 eV): m/z 599.2 [M+Na]+, 577.2 [M+H]+; HRMS (ESI): m/z calcd for
C38H28N2O4 (Mw = 576.64 gmolÀ1) 577.2127 [M+H]+; found: 577.2122.
studies to explore the scope and limitations of chiral self-
sorting in self-assembly processes to elucidate general prin-
ciples that ensure narcissistic self-recognition or social self-
discrimination.
Synthesis of [Pd2(1)4]
di(methoxymethoxy)-3,3’-bis(3-ethyndiyl-pyridyl)-1,1’-binapththyl (5 mg,
8.67 mmol) in CD2Cl2 (0.6 mL) was added a solution of [Pd(CH3CN)4]-
(BF4)2 (1.93 mg, 5.67 mmol) in CD3CN (0.2 mL). The resulting mixture
ACHTUGNTREN(UNNG BF4)4: To a solution of (P)- or (M)-, or (rac)-2,2’-
Experimental Section
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
Reactions under inert gas atmosphere were performed under argon by
using standard Schlenk techniques and oven-dried glassware. Thin layer
chromatography was performed on aluminum TLC plates silica gel 60
F254 from Merck. Detection was carried out under UV light (l=254 and
366 nm). Products were purified by column chromatography on silica gel
60 (70–230 mesh) from Merck. The 1H and 13C NMR spectra were re-
corded on a Bruker DRX 500 spectrometer at 293 K, at 500.1 and
was stirred for one day at RT or for 3 h at 558C to get the desired com-
plex in quantitative yield. 1H NMR (400 MHz, CD2Cl2/CD3CN 3:1,
3
293 K): d=9.01 (s, 8H, H17), 8.94 (d, JH16,H15 =5.6 Hz, 8H, H16), 8.04 (s,
8H, H4), 8.01 (ddd, 3JH14,H15 =8.0, 4JH14,H16 =1.9, 4JH14,H17 =1.2 Hz, 8H,
3
H14), 7.75 (d, 3JH5,H6 =8.2 Hz, 8H, H5), 7.52 (dd, 3JH15,H14 =8.0, JH15,H16
=
3
3
4
5.6 Hz, 8H, H15), 7.43 (ddd, JH6,H5 =8.1, JH6,H7 =6.9, JH6,H8 =1.1 Hz, 8H,
H7), 7.26 (ddd,3JH7,H8 =8.6, 3JH6,H7 =6.9, 4JH6,H8 =1.0 Hz, 8H, H6), 6.98 (d,
3JH8,H7 =8.6 Hz, 8H, H8), 4.94 (d, 2JH9a,H9b =À5.9 Hz, 8H, H9a), 4.84 (d,
2JH9b,H9a =À5.9 Hz, 8H, H9b), 2.46 (s, 24H, H10); 1H DOSY NMR
(500.1 MHz, CD3CN, 293 K): d=7.929ꢅ10À10 m2 sÀ1; MS (ESI, 10 eV): m/
125.8 MHz, on
100.6 MHz, or
a
a
Bruker AM 400 at 293 K, at 400.1 MHz and
Bruker Avance 300 at 293 K at 300.1 MHz and
75.5 MHz, respectively. The 1H NMR chemical shifts are reported in d
scale (ppm) relative to residual nondeuterated solvent as the internal
standard. The 13C NMR chemical shifts are reported in d scale (ppm) rel-
ative to deuterated solvent as the internal standard. Signals were assigned
on the basis of 1H, 13C, heteronuclear multiple-quantum correlation
(HMQC), and heteronuclear multiple-bond correlation (HMBC) NMR
z 1346.5 {[Pd2(1)4]
Crystal-structure determination: X-ray crystallographic analysis of
[Pd2{(P)-1}4](BF4)4: Data were collected on Bruker X8-Kappa-
(BF4)2}2+, 868.6 {[Pd2(1)4](BF4)}3+
ACHTUNGTERNNUNG CAHTUNGTRENNUNG .
A
a
APEX II diffractometer equipped with a low-temperature device (Kryo-
felx I, Bruker AXS GmbH, Karlsruhe) by using graphite monochromatic
MoKa radiation (l=0.71071 ꢆ). The structure was solved by direct meth-
ods (SHELXL-97) and refined by full-matrix least squares on F2
(SHELXL-97).[15] All nonhydrogen atoms were refined anisotropically.
Hydrogen atoms at carbon atoms were placed in calculated positions and
refined isotropically by using a riding model.
experiments. Mass spectra were recorded at
a microOTOF-Q or a
Apex IV FTICR from Bruker. Elemental analyses were carried out with
a HeraeusVario EL. However, CHN analyses could only be conducted
with fluorine-free compounds. Most solvents were dried and distilled ac-
cording to standard procedures, and were stored under argon. Enantio-
pure 2,2-dihydoxy-1,1’-binaphthyl and 3-ethynylpyridine were used as re-
ceived (Alfa Aesar and Sigma–Aldrich). (P)-, (M)-, and (rac)-2,2-di(me-
Crystal
dimensions
0.12ꢅ0.08ꢅ0.05 mm;
colorless
plates;
152H112B4F16N8O16Pd2; Mw =2866.54 gmolÀ1; triclinic; space group P1;
¯
C
thoxymethoxy)-1,1’-binaphthyl were prepared by
a
literature proce-
dure.[13, 14]
a=15.3148(5), b=16.5223(5), c=18.8622(5) ꢆ; a=69.520(2), b=
67.529(2), g=88.238(2)8; V=4102.3(2) ꢆ3; Z=1; 1=1.160 gcmÀ3; m=
Synthesis of (P)-, (M)-, and (rac)-3,3’-diiodo-2,2’-di(methoxymethoxy)-
1,1’-binaphthyl:[14] To a solution of (P)-, (M)-, or (rac)-2,2’-di(methoxy-
methoxy)-1,1’-binaphthyl (2.12 g, 5.66 mmol) in dry THF (30 mL) at
À788C, sec-butyllithium (16.58 mL, 23.21 mmol, 1.4m in cyclohexane)
was added, and the mixture was stirred for 1.5 h. After that time, iodine
(8.62 g, 33.97 mmol) dissolved in dry THF (15 mL) was added, and the
resulting solution was stirred at À788C for 15 h and for 3 h at RT. The re-
action was quenched with methanol and saturated aqueous Na2SO3 solu-
0.294 mmÀ1; F
ACHTNUTRGEN(UGN 000)=1464; 48156 reflections measured (2qmax =28.008;
33210 unique, Rint =0.0306, completeness=99.3%); final R indices [I>
2s(I)]; R1 =0.0722; wR2 =0.1899; R indices (all data): R1 =0.1022, wR2 =
0.2057; GOF=0.975 for 1791 parameters and 330 restraints; largest diff.
peak and hole 1.710/À0.975 eꢆ3, absolute stereochemical parameter X=
0.00(2). CCDC-934122 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cam-
Chem. Eur. J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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