=
169.34, 168.90, 168.48, 167.41 (C O), 69.79, 69.46, 68.97, 68.83,
68.75, 68.61 (CH), 16.94, 16.64, 16.32, 16.28, 16.21 (CH3).
needle crystals were obtained. 1H NMR d (CD3CN) 7.25 (broad,
=
=
8H, CH C–H), 6.98 (t, 8H, J = 7.2 Hz, CH C–H), 6.83 (t, 4H,
=
(3). (S,S,R,R,S,R)- or (R,R,S,S,R,S)-(CH3CHC(O)O)6 (6).
J = 7.2 Hz, CH C–H), 4.93 (q, 6H, J = 7.0 Hz, CHMe), 1.49
1
13
=
Yield 8 mg, 0.5%. H NMR d (CDCl3) 5.38 (q, 1H, J = 7.0 Hz,
(d, 18H, J = 7.0 Hz, CH3); C NMR d (CD3CN) 168.9 (C O),
CHMe), 5.31 (q, 1H, J = 7.0 Hz, CHMe), 5.25 (q, 1H, J = 7.0 Hz,
CHMe), 5.22 (q, 1H, J = 7.0 Hz, CHMe), 5.18 (q, 1H, J = 7.0 Hz,
CHMe), 5.10 (q, 1H, J = 7.0 Hz, CHMe), 1.57 (d, 3H, J = 7.0 Hz,
Me), 1.54 (d, 3H, J = 7.0 Hz, Me), 1.53 (d, 3H, J = 7.0 Hz,
128.6, 128.4, 127.9, 127.2 (C6H5), 68.8 (CH), 16.9 (CH3).
Summary of crystal data
Me), 1.51 (d, 6H, J = 7.0 Hz, Me), 1.48 (d, 3H, J = 7.0 Hz, Me);
13
DMAP:BPh3 (1): C25H25BN2, M = 364.28, orthorhombic, space
=
C NMR d (CDCl3) 169.46, 169.06, 169.03, 168.67 (C O), 70.00,
˚
−1
group Pbca, a = 15.230(1), b = 11.7129(8), c = 22.515(2) A,
69.69, 69.46, 69.42, 68.94, 68.83 (CH), 16.83, 16.73, 16.49, 16.42,
16.35 (CH3).
(4). (S,R,R,S,R,R)- or (R,S,S,R,S,S)-(CH3CHC(O)O)6 (7).
3
˚
V = 4016.4(5) A , T = 95(2) K, Z = 8, l = 0.015 mm ,
48843 reflections collected, 3750 independent (Rint = 0.054), R1 =
0.044 for 3200 reflections with I > 2r(I). A6Na+BPh4−(CH3CN)2
1
Yield 5 mg, 0.3%. H NMR d (CDCl3) 5.33 (q, 2H, J = 7.0 Hz,
¯
(2), C40H38BN2NaO12, M = 772.52, triclinic, space group P1,
CHMe), 5.26 (q, 2H, J = 7.0 Hz, CHMe), 5.20 (q, 2H, J = 7.0 Hz,
CHMe), 1.53 (d, 6H, J = 7.0 Hz, Me), 1.50 (d, 6H, J = 7.0 Hz,
Me), 1.48 (d, 6H, J = 7.0 Hz, Me); 13C NMR d (CDCl3) 169.03,
◦
˚
a = 12.920(1), b = 13.473(1), c = 13.977(2) A, a = 80.972(4) ,
◦
◦
3
˚
b = 64.021(4) , c = 63.137(5) , V = 1948.6(3) A , T = 150(2)
K, Z = 2, l = 0.106 mm−1, 44653 reflections collected, 6794
independent (Rint = 0.045), R1 = 0.050 for 4646 reflections
with I > 2r(I). A6-(CH2C(O)O)6 (3). C12H12O12, M = 348.22,
monoclinic, space group P21/c, a = 7.668(1), b = 5.901(1), c =
=
168.95, 168.84 (C O), 69.75, 69.51, 68.87 (CH), 16.82, 16.78,
16.31 (CH3).
(5). (S,R,S,R,R,R)- or (R,S,R,S,S,S)-(CH3CHC(O)O)6 (8).
Yield 0.32 g, 22%. 1H NMR d (CDCl3) 5.37 (q, 1H, J = 7.0 Hz,
CHMe), 5.32 (q, 1H, J = 7.0 Hz, CHMe), 5.26 (q, 1H, J = 7.0 Hz,
CHMe), 5.22 (q, 1H, J = 7.0 Hz, CHMe), 5.20 (q, 1H, J = 7.0 Hz,
CHMe), 5.18 (q, 1H, J = 7.0 Hz, CHMe), 1.56 (d, 3H, J = 7.0 Hz,
Me), 1.55 (d, 3H, J = 7.0 Hz, Me), 1.55 (d, 3H, J = 7.0 Hz,
Me), 1.51 (d, 6H, J = 7.0 Hz, Me), 1.49 (d, 3H, J = 7.0 Hz, Me);
13C NMR d (CDCl3) 169.29, 169.06, 169.04, 168.97, 168.70, 168.28
◦
3
˚
˚
16.004(3) A, b = 102.408(9) , V = 707.3(2) A , T = 150(2)
K, Z = 2, l = 0.151 mm−1, 17673 reflections collected, 1618
independent (Rint = 0.033), R1 = 0.041 for 1313 reflections
with I > 2r(I). (S,S,R,R,R,R)-(CH3CHC(O)O)6 (5): C18H24O12,
M = 432.37, monoclinic, space group P21/n, a = 8.432(1), b =
◦
3
˚
˚
16.513(2), c = 14.964(2) A, b = 93.048(5) , V = 2080.7(4) A ,
T = 150(2) K, Z = 4, l = 0.118 mm−1, 34054 reflections collected,
4751 independent (Rint = 0.040), R1 = 0.035 for 3455 reflections
with I > 2r(I). (S,R,R,R,R,R)-(CH3CHC(O)O)6 (9): C18H24O12,
=
(C O), 69.39, 69.16, 69.06, 68.85, 68.71 (CH), 16.67, 16.53, 16.49,
16.41, 16.17 (CH3).
(6). (S,R,S,R,S,R)-(CH3CHC(O)O)6 (11). Yield 54 mg, 3.7%.
1H NMR d (CDCl3) 5.25 (q, 6H, J = 7.0 Hz, CHMe), 1.50 (d,
M = 432.37, orthorhombic, space group P212121, a = 10.663(2),
3
˚
˚
18H, J = 7.0 Hz, Me); 13C NMR d (CDCl3) 168.97 (C O), 68.93
b = 11.967(3), c = 16.489(4) A, V = 2104.1(8) A , T = 150(2)
K, Z = 4, l = 0.116 mm−1, 16936 reflections collected, 2124
independent (Rint = 0.025), R1 = 0.033 for 1925 reflections with
=
(CH), 16.56 (CH3).
2. Using the [(CH3CHC(O)O)6]NaBPh4 prepared from L-lactide
(2.01 g, 2.87 mmol) treated with the procedure described in step
1, complex 9, 10 and 11 were isolated and separated by column
chromatography.
(1). (S,R,R,R,R,R)- or (R,S,S,S,S,S)-(CH3CHC(O)O)6 (9).
Yield 32 mg, 2.6%. 1H NMR d (CDCl3) 5.34 (q, 1H, J = 7.0 Hz,
CHMe), 5.31 (q, 1H, J = 7.0 Hz, CHMe), 5.29 (q, 1H, J = 7.0 Hz,
CHMe), 5.26 (q, 1H, J = 7.0 Hz, CHMe), 5.19 (q, 1H, J = 7.0 Hz,
CHMe), 5.17 (q, 1H, J = 7.0 Hz, CHMe), 1.60 (d, 3H, J = 7.0 Hz,
Me), 1.53 (d, 3H, J = 7.0 Hz, Me), 1.53 (d, 6H, J = 7.0 Hz,
Me), 1.52 (d, 3H, J = 7.0 Hz, Me), 1.51 (d, 3H, J = 7.0 Hz, Me);
13C NMR d (CDCl3) 169.60, 169.06, 168.75, 168.56, 168.54, 168.24
I
> 2r(I). Na[(S,R,S,R,S,R)-(CH3CHC(O)O)6]BPh4·CH3CN
(12): C44H47O12NBNa, M = 815.62, monoclinic, space group
◦
˚
P21/n, a = 9.986(2), b = 19.900(3), c = 21.545(4) A, b = 90.376(6) ,
3
−1
˚
V = 4281(1) A , T = 150(2) K, Z = 4, l = 0.100 mm , 41693
reflections collected, 7541 independent (Rint = 0.052), R1 = 0.042
for 4755 reflections with I > 2r(I).
CCDC reference numbers 271310, and 651113–651116.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b709081a
=
(C O), 69.88, 69.66, 69.37, 69.08 (CH), 16.79, 16.64, 16.59, 16.55,
16.51, 16.45 (CH3).
Acknowledgements
(2). (S,S,S,S,S,S)-(CH3CHC(O)O)6 (10). Yield 70 mg, 5.6%. 1H
NMR d (CDCl3) 5.36 (q, 6H, J = 7.0 Hz, CHMe), 1.55 (d, 18H,
We thank the Department of Energy, Office of Basic Sciences,
Chemical Division, for support of this work. We also thank
Professor C. Hadad for assistance with computations and Dr
Maren Pink of Indiana University for the synchrotron data
collection of C25H25BN2 at the Advanced Photon Source at
Argonne National Laboratory. The Advanced Photon Source
is supported by the U.S. Department of Energy, Basic Energy
Sciences, Office of Science, under Contract No. W-31-109-Eng-
38. ChemMatCARS Sector 15 is principally supported by the
National Science Foundation/Department of Energy under grant
number CHE0087817 and by the Illinois Board of Higher
Education.
J = 7.0 Hz, Me); 13C NMR d (CDCl3) 168.39 (C O), 69.17 (CH),
=
16.89 (CH3).
3. Na[(S,R,S,R,S,R)-(CH3CHC(O)O)6]BPh4·CH3CN (12). To
the mixture of (S,R,S,R,S,R)-(CH3CHC(O)O)6 (25 mg,
0.058 mmol) and NaBPh4 (20 mg, 0.058 mmol) was added 1 ml
of C6H6 and the reaction mixture was stirred at 90 ◦C overnight.
The reaction suspension was filtered off and the remaining solid
was washed with benzene (2 × 3 ml), and dried under vacuum,
yielding white solid (32 mg, 71%). The solid was redissolved in
CH3CN and with slow evaporation, crystallographic quality long-
4820 | Dalton Trans., 2007, 4811–4821
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The Royal Society of Chemistry 2007
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