58
A. El-Qisairi, P.M. Henry / Journal of Organometallic Chemistry 603 (2000) 50–60
posed. Anal. Calc. for Pd2C60H48O3N2P2B2F8: C, 55.72;
H, 3.74; N, 2.17; P, 4.79. Found: C, 56.72; H, 3.83; N,
2.16; P, 4.91%. H-NMR (DMSO): l 1.76 (s), 2.06 (s),
H, 3.38; N, 2.94; P, 4.34. Found: C, 40.37; H, 3.76; N,
2.91; P, 4.34%. H-NMR (DMSO): l 1.63 (s), 1.75 (s),
1
1
2.05 (s), 2.20 (dd), 2.30 (s.br), 4.10 (td.br), 04.37 (td.br),
6.31 (s), 6.57 (s), 6.87 (d), 7.14 (t), 7.37 (m), 7.56 (m),
7.84 (m), 7.95 (d). 13C-NMR (DMSO): l 1.13, 22.40,
26.45, 29.30, 74.82, 75.94, 97.02, 97.80, 99.00, 108.68,
118.10, 126.29, 127.20, 127.37, 127.50, 127.86, 128.13,
128.59, 128.97, 129.27, 130.76, 131.73, 132.66, 132.89,
133.16, 133.72, 135.85, 136.43, 167.36, 177.74, 188.11.
31P-NMR (DMSO): l 22.8 and 22.9. FTIR (Nujol):
3030 (w), 02984 (vs), 2932 (vs), 2890 (m), 2365 (m),
2350 (m), 1660 (vs), 1582 (vs), 1482 (vs), 1438 (vs), 1386
(m), 1244 (m), 1160– 998 (vs.br), 881 (s), 818 (m), 746
6.53 (s), 6.87 (dd), 7.05 (t), 7.20 (t), 7.52 (m), 7.65 (m),
7.74 (br,d), 7.80 (t), 7.91 (m.br). 13C-NMR (DMSO): l
1.2, 22.5, 91.9, 95.7, 117.9, 118.9, 122.7, 123.6, 123.8,
124.6, 125.3, 125.9, 126.0, 126.1, 126.4, 126.5, 126.7,
127.0, 127.1, 127.2, 127.3, 127.4, 127.6, 127.7, 127.8,
127.8, 128.0, 128.2, 128.3, 128.4, 128.8, 129.0, 129.1,
130.0, 131.6, 132.2, 132.9, 133.8, 134.1, 135.0, 135.1,
139.0, 161.8, 162.5, 171.3, 174.7, 175.4. 31P-NMR
(DMSO): l 34.37 (s). FTIR (Nujol): 3028 (w), 2971
(vs), 2882 (vs), 2842 (vs), 2328 (m), 2293 (m), 1658 (m),
1608 (m), 1584 (m), 1554 (m), 1462 (vs), 1377 (vs), 1311
(m), 1161 (sh), 1130–995 (vs.br), 872 (m), 815 (m), 745
(s), 693 (vs), 525 (vs) cm−1
.
4.3.5. Diacetonitrile-2,4,6-heptanetrione-v-
(s), 719 (s), 695 (vs), 522 (vs), 500 (m) cm−1
.
(−)-2,3-O-isopropylidene-2,3-dihydroxy-
1,4-bis(diphenylphosphino)butane dipalladium(II)
tetrafluoroborate ([Pd2(MeCN)2(HpT)(−)DIOP](BF4)2)
The preparation of this yellowish-brown compound
was accomplished using the previous procedure with
2,4,6-heptanetrione, [Pd(CH3CN)4](BF4)2, triethylamine
and (−)-DIOP as starting materials: yield 71%; m.p.
108–110°C (decomposed). This compound was charac-
4.3.8. Diacetonitrile-2,4,6-heptanetrione-v-
(S)-(−)-2,2-bis(diphenylphosphino)-1,1%-binaphthyl
dipalladium(II) tetrafluoroborate
([Pd2(MeCN)2(HpT)(S)BINAP](BF4)2)
This yellow compound was prepared using the proce-
dure described above using 2,4,6-heptanetrione di-
sodium salt, [Pd(CH3CN)4](BF4)2, and (S)-(−)-BINAP
as starting materials: yield 87%. This compound was
1
terized by H-, 13C- and 31P-NMR.
1
characterized by H-, 13C- and 31P-NMR.
4.3.6. Diacetonitrile-1-phenyl-6,6,6-trifluoro-
1,3,5-hexanetrione-v-(+)-2,3-O-isopropylidene-
2,3-dihydroxy-1,4-bis(diphenylphosphino)-
4.4. Oxidation reactions
4.4.1. General procedure
butanedipalladium(II)tetrafluoroborate
The mmoles of reagents and the total amount of gas
uptake for each run are given in Table 4. Enantioselec-
tivities were measured using about a 0.3 mol ratio if
Eu(hfc)3 to product. The yields of the chlorohydrins for
the propene and 1-butene runs were calculated from the
areas of the of the GLC peaks using internal standards.
([Pd2(MeCN)2(PFHT)(+)DIOP](BF4)2)
This yellow compound was prepared using the proce-
dure described above with 1-phenyl-6,6,6-trifluoro-
1,3,5-hexanetrione, [Pd(CH3CN)4](BF4)2, triethylamine
and (+)-DIOP as starting material: yield 76%; m.p.
87–89°C. This compound was characterized by 1H-,
13C- and 31P-NMR.
4.4.2. Oxidation of propene
4.3.7. Diacetonitrile-1-phenyl-1,3,5-hexanetrione-v-
(S)-(−)-2,2-bis(diphenylphosphino)-1,1-binaphthyl
dipalladium(II) tetrafluoroborate
In the aqueous mixed solvent runs (1–3), acetone
was isolated as 2,4-dinitrophenylhydrazone derivative
and identified by H-NMR. The chlorohydrin products
1
([Pd2(MeCN)2(PHT)(S)BINAP](BF4)2)
were isolated by continuous extraction with Et2O for 3
days. The ether was dried over anhydrous MgSO4 and
then evaporated. Two products with similar retention
times were detected by GLC in a 2.8:1.0 ratio. The first
product was collected by preparative GLC and iden-
To a stirred solution of [Pd(CH3CN)4](BF4)2 (0.238
g, 0.536 mmol) in 15 ml of dry CH3CN under argon,
was added dropwise 1-phenyl-1,3,5-hexanetrione
(0.0547 g, 0.268 mmol), followed by 10 drops of
(CH3)3N. The color changed immediately to orange.
The reaction mixture was stirred for 30 min at r.t. Then
(S)-(−)-BINAP (0.167 g, 0.268 mmol) in 3 ml of C6H6
was added to the reaction mixture. The reaction mix-
ture was stirred for an additional 12 h. The solvent was
removed by a rotary evaporator to give a pasty red
residue. The residue was washed with anhydrous Et2O
(3×30 ml). The greenish-yellow solid was dried under
vacuum: yield 0.310 g (92.9%). M.p. 135–136°C decom-
1
tified as 1-chloro-2-propanol. H-NMR (CDCl3): l 1.26
(d, 3H), 2.19 (d.br, OH), 3.43 (dd, 1H), 3.57 (dd, 1H),
and 3.99 (m, 1H). 13C-NMR (CDCl3): l 20.24, 51.61,
67.66. Because of similar retention times preparative
GLC gave a 1:1 mixture of 1-chloro-2-propanol and the
second product. The second product was identified as
2-chloro-1-propanol. 1H-NMR (CDCl3) for the mix-
ture: l 1.26 (d, 3H), 1.50 (d, 3H), 2.00 (br, OH), 2.19
(br, OH), 3.43 (dd, 1H), 3.57 (dd, 1H), 3.65 (dd, 1H),