220
U. Nagel - Ch. Roller •Der Einfluß nicht koordinierter Stereozentren
Säulenlänge: 94 cm, Kieselgel: Merck 60 H, 0.005-0.040
mm. 600 g) aufgetragen. Als erstes verlassen die C2-
Isomeren die Säule, danach das C,-Isomere, wobei das
gleiche Elutionsmittelgemisch verwendet wird.
(w, CH2-Valenz), 2973 (w, CH3-Valenz). - MS (FD)[m/z]:
952.3 M+-I, 853.8 M+-I-Boc, 341.2 PPhC2H4POPh2+.
[(P(R),3R, 4R,P'(S))-1 -tert. -Butyloxycarbonyl-3,4-bis-
{[2-(methyl-phenyl-P(S)-oxophosphanyl)-ethylJphenyl-
phosphanyl}pyrrolidin-P,P']-palladiumdiiodid (8c)
[(P(R,S), 3R,4R,P'(R,S))-1 -tert.-Butyloxycarbonyl-3,4-
bis{[2-(methyl-phenyl-P(S)-oxophosphanyl)-ethyl]-
phenyl-phosphanyl}pyrrolidin-P,P']-palladiumdiiodid
(8a-c)
Ausbeute: 381 mg (11%) - [a]589= +57.38° (c, 0.61,
CH2C12). - 1H-NMR (CDC13): 1.18,1.22, 1.32 (je s, 9H,
Boc-CH3), 1.6 (d, POCH3, 7ph = 10 Hz), 2.03-4.05 (m,
14H, CH u. CH2), 7.0-8.14 (m, 20H, Ph-H). - 13C {'H }-
NMR (CDC13): 15.35 (d, P-CH2, 7CP = 18.8 Hz), 20.40
(d, Jcp = 35.8 Hz, PO-CH3), 28.7 (d, JCP = 13.2 Hz,
PO-CH2), 29.5 (d, Jcp = 16.35 Hz, Boc-CH3), 42.45,
43.77 (je d, 7Cp = 18.24 Hz, Boc-Rotamere, N-CH2),
49.36, 50.18 (je d, JCP = 12.58 u. JCP = 15.73 Hz, Boc-
Rotamere, P-CH), 80.9 (s, quart.Boc-C), 128.2-135.4 (m,
Ph-C), 154.8 (s, Boc-CO). - 3iP {'H }-N M R (Aceton): 2
Boc-Rotamere ABCD-Spektren, AB-Teil (Pd-P) und CD-
Teil nicht separierbar: 36.53-45.54 Multiple« - IR (KBr,
cm-1): 692, 726, 742 (s, Ph out of plane), 1117, 1175
(s, P=0), 1401 (s breit, CH3-Def.), 1436 (s, Ph-P), 1680
(s, C=0-Boc), 2926 (w, CH2-Valenz), 2969, 3052 (w,
CH3-Valenz). - MS (FD)[m/z]: 851.9 M+-I-Boc, 341.2
PPhC2H4POPh2+.
Einwaage 2.34
g (3.26 mmol) Ligand Nr la-c.
Ausbeute: 1.46 g (42%) Diastereomerengemisch 8a-c:
8a : 8b : 8c = 4.2% : 69.6% : 26.2%.
[(P(S), 3R,4R,P'(S))-1 -tert. -Butyloxycarbonyl-3,4-
bis{[2-(methyl-phenyl-P(S)-oxophosphanyl)-ethyl]-
phenxl-phosphanyl]pyrrolidin-PP']-pcdladiumdiiodid
(8a )'
Ausbeute: 0.062 g (1.8%) 8a. - 'H-NM R (Aceton):
1.12 (s, 9H, Boc-CH3), 2.17-3.47 (m 14H, CH2 u. CH),
7.3-7.9 (m, 20H, Ph-H) - 13C {'H }-N M R (Aceton): 15.2
(d, PO-CH3, Jcp = 12 Hz), 16.35 (dd, JCP = 10 Hz für
beide, P-CH2), 27.31 (s, PO-CH2), 28.36 (s, Boc-CH3),
44.34, 44.79” (t, Boc-Rotamer, N-CH2, je 7CP = 15-1
Hz), 79.74 (s, quart.Boc-C), 126.47-136.39 (m, Ph-C),
154.12 (s, Boc-CO) - 3IP {'H }-N M R (Aceton): ABCD-
Spektrum, ca. 35.3, ca. 35.9 (je d, 7P(o)p = ca. 55.7 Hz),
ca. 40.76, ca. 40.93 (m, 7PP. = ca. 21.7 Hz) - IR (KBr,
cm-1): 694, 742 (s, Ph-H out of plane), 1117, 1178 (s,
P=0), 1396 (s breit, CH3-Def.), 1436 (s, Ph-H), 1688 (s,
CO-Boc), 2855, 2926 (w, CH2-Valenz), 2962, 3053 (w,
CH3-Def.) - MS(FD)[m/z]: 952.3 M +-I, 851.9 M+-I-Boc,
341.2 PPhC2H4POPh2+.
[(P(R,S),3R,4R,P'(R,S))-l-tert.-Butyloxycarbonyl-3,4-
bis{[2-(methyl-phenyl-P(R)-oxophosphanyl)-ethyl]-
phenyl-phosphanyl}pyrrolidin-P,P']-palladiumdiiodid
(9a-c)
Einwaage 0.94 g (1.31 mmol) Ligand 2a-c. Ausbeute:
0.798 g (56%) Diastereomerengemisch 9a-c:
9a : 9b : 9c = 5% : 62.7% : 32.3%.
[(P(S),3R,4R,P'(S))-1 -tert. -Butyloxycarbonyl-3,4-bis-
{[2-(methyl-phenyl-P(R)-oxophosphanyl)-ethylJphenyl-
phosphanyl}pyrrolidin-PP']-palladiumdiiodid (9a)
[(P(R),3R,4R,P'(R))-l-tert.-Butyloxycarbonyl-3,4-
bis{[2-(methyl-phenyl-P(S)-oxophosphanyl)-ethyl]-
phenyl-phosphanyl} -pyrrolidin-P, P ']-palladiumdiiodid
(8b )'
Ausbeute: 40 mg (2.8%). - 'H-NMR (CDC13): 1.15-
1.34 (m, 9H, Boc-CH3), 1.58 (d, 3H, POCH3, 7PH = 2.5
Hz), 2.10-3.81 (m, 14H, CH2 u. CH), 1.2-1.1 (m, 20H,
Ph-H). - ,3C {'H }-N M R (CDC13): 15.23 (s, PO-CH3),
19.12 (s, P-CH2), 28.43 (dd, PO-CH2, J nicht ables-
bar), 30.5 (s, Boc-ch3), 80.15 (s, quart.Boc-C), 128.33-
132.5 (m, Ph-C). - 31P {'H }-N M R (Aceton): 33.8-34.0
Multiplett, AB-Teil u. C-Teil nicht aufgelöst IR (KBr,
cm-1): 694, 743 (m, Ph-H out of plane), 1119, 1177
(s, P=0), 1393 (s, CH3-Def.), 1435 (m, Ph-P), 1693,
1728 (s, C=0-Boc), 2854, 2874, 2926 (w, CH2-Valenz),
2961, 3053 (w, CH3-Valenz). - MS (FAB, 50°)[tn/z(%)]:
951.1 (100) M+-I, 896 (15) M+-I-C4H8, 824.2 (10) M+-
21, 602.2 (18) M+-2I-C4H8-C2H4POCH3C6H5, 275 (100)
PC6H,C2H4POCH3C6Hv
Ausbeute: 1.016 g (29%) - Schmp.: ca. 180°C Zer-
setzung, [a ]589 = +102.30° (c, 0.61, CH2C12) 'H-NM R
(CDC13): 1.26 (s, 9H, Boc-CH3), 1.66 (d, POCH3, /PH
= 10 Hz), 2.34-3.5 (m, 14H, CH2 u. CH), 7.25-7.71 (m,
20H, Ph-H). - l3C {'H }-N M R (CDC13): 14.5-16.1 (m,
P-CH2), 17.14 (d, PO-CH3, Jcp = 69.95 Hz), 28.07 (s,
Boc-CH3), 30.0 (d, PO-CH2, Jcp = 27 Hz), 42.8-43.1 (m,
N-CH-)), 51.7-52.38 (m, P-CH), 80.5 (s, quart.Boc-C),
128.12-132.2 (m, Ph-C), 153.6 (s, Boc-CO). - 31P {‘H }-
NMR (Aceton): ABCD-Spektrum: 35.9,36.08 (je d,yP(0)p
= 55.7 Hz), 40.76, 40.93 (m, JPP. = 21.7 Hz). - IR (KBr.
cm-1): 690, 724. 739 (s, Ph-H out of plane), 1078, 1193
(s, P=0), 1437 (s, Ph-P), 1683 (s, C=0-Boc), 2876, 2925
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