G. E. Moreno et al. / Tetrahedron Letters 45 (2004) 4245–4248
4247
194 ꢁC, ½a þ 131:0 (c 1, CHCl3). 1H NMR (400 MHz)
and Kee and co-workers4 (Table 2, entry 3) with our
results (Table 2, entries 4, 5, 7 and 8).
D
d ¼ 8:26 (d, J ¼ 8 Hz, 1H), 7.93–7.14, 16 H), 5.75
(d, J ¼ 9:2 Hz, 1H), 4.43 (c, J ¼ 6:8 Hz, 1H), 4.07 (m,
1H), 3.61 (s, 1H), 2.29 (m, 2H), 2.17 (m, 1H), 1.78
(d, J ¼ 7:2 Hz, 3H), 1.76 (m, 2H), 1.53 (d, J ¼ 6:8 Hz,
3H), 1.34 (m, 1H), 1.25 (m, 1H). 13C NMR (400 MHz)
In conclusion, we obtain moderate diastereoselectivities
on the carbonyl phosphonylation of aldehydes using the
N,N0-bis-[(S)-a-phenylethyl]-bicyclic phosphorous acid
diamides 2 prepared fromthe (1 S,2S,10S,100S)- and
(1R,2R,10S,100S)-trans-N,N0-bis[(S)-a-phenylethyl]-1,2-
diamino-cyclohexane 1. Contrary to our expectations,
the conformational preferences of the a-phenylethyl
group have no influence over the stereochemistry of the
newly generated a-stereocentre.
d ¼ 134:5, 133.3, 130.8, 128.8–123.7, 70.9 (d, JCP
¼
123:0 Hz), 62.3 (d, JCP ¼ 9:1 Hz), 60.8 (d, JCP ¼ 6:0 Hz),
54.8 (d, JCP ¼ 4:5 Hz), 52.3, 30.8 (d, JCP ¼ 7:6 Hz), 29.7
(d, JCP ¼ 6:1 Hz), 24.4 (d, JCP ¼ 4:6 Hz), 23.16, 19.7 (d,
JCP ¼ 7:6 Hz). 31P NMR d ¼ 36:6. Mass spectra (M þ Na)þ
calcd 547.2490, found 547.2495 (ES þ ). X-ray structure:
colourless needle, 0.65 · 0.24 · 0.20 mm3, C33H37N2O2P,
monoclinic, P21, a ¼ 11:1340ð12Þ, b ¼ 10:092ð2Þ,
0
ꢂ
c ¼ 13:1275ð15Þ A, b ¼ 96:716ð8Þꢁ, Z ¼ 2, Z ¼ 1. Bruker
ꢂ
P4 diffractometer using Mo Ka radiation (k ¼ 0:71073 A),
T ¼ 296ð1Þ K, 7514 reflections measured up to 2h ¼ 55ꢁ,
3937 independent data (Rint ¼ 2:60%) for 434 refined
parameters. The structure was solved and refined using
standard methods8 with data corrected for absorption effect
(transmission factors: 0.623 to 0.662). Final R indices:
R1 ¼ 3:87% for 2903 reflections having Fo > 4rðFoÞ and
wR2 ¼ 11:07% for all data. Absolute configuration fromthe
refinement of a Flack parameter: x ¼ À0:01ð11Þ. The
crystallographic data have been deposited with the CCDC
(number 226194).
Acknowledgements
We thank CONACYT for financial support (Project No
39500-Q and Grant No 91276).
References and notes
(3aS,7aS)-3-Methyl-1-[2-oxo-1,3-bis-[(S)-a-phenylethyl]-
octahydro-2k5-benzo[1,3,2]diazaphosphol-2-yl]-butan-1-ol,
3f minor isomer. Colourless crystals, mp ¼ 194–196 ꢁC,
1. (a) Kirby, A. J.; Warren, S. G. In The Organic Chemistry of
Phosphorus; Elsevier: New York, 1967; (b) Pudovik, A. N.;
Konovalova, I. V. Synthesis 1979, 81–96.
½a þ 13:10 (c 1, CHCl3). 1H NMR (300 MHz) d: 7.67–
D
2. (a) Rowe, B. J.; Spilling, C. D. Tetrahedron: Asymmetry
2001, 12, 1701–1708; (b) Groaning, M. D.; Rowe, B. J.;
Spilling, C. D. Tetrahedron Lett. 1998, 39, 5485–5488; (c)
Blazis, V. J.; Koeller, K. J.; Spilling, C. D. Tetrahedron:
Asymmetry 1994, 5, 499–502; (d) Blazis, V.; de la Cruz, A.;
Koeller, K.; Spilling, C. D. Phosphorus, Sulfur, Silicon
Relat. Elem. 1993, 75, 159–162; (e) Koeller, K. J.; Spilling,
C. D. Tetrahedron Lett. 1991, 32, 6297–6300; (f) Cain, M.
J.; Baird, C. A.; Kee, T. P. Tetrahedron Lett. 1994, 35,
8671–8674; (g) Sum, V.; Kee, T. P.; Thornton-Pett, M. J.
Chem. Soc., Chem. Commun. 1994, 743–744; (h) Davies, S.
D.; Mitchel, M.; Cain, C. P.; Devitt, P. G.; Taylor, R. J.;
Kee, T. P. J. Organomet. Chem. 1998, 550, 29–57; (i) Dux-
bury, J. P.; Cawley, A.; Thorton-Pett, M.; Wantz, L.;
Warne, J. N. D.; Greatrex, R.; Brown, D.; Kee, T. P.
Tetrahedron Lett. 1999, 40, 4403–4406; (j) Yokomatsu, T.;
Yamagishi, T.; Shibuya, S. Tetrahedron: Asymmetry 1993,
4, 1783–1784; (k) Yokomatsu, T.; Yamagishi, T.; Shibuya,
S. J. Chem. Soc., Perkin Trans. 1 1997, 1527–1534; (l)
Yamagishi, T.; Yokomatsu, T.; Suemune, K.; Shibuya, S.
Tetrahedron 1999, 55, 12125–12136; (m) Sasai, H.;
Bougauchi, M.; Arai, T.; Shibasaki, M. Tetrahedron Lett.
1997, 38, 2717–2720; (n) Arai, T.; Bougauchi, M.; Sasai, H.;
Shibasaki, M. J. Org. Chem. 1996, 61, 2926–2927; (o)
Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187–
2209.
7.17 (m, 10H), 4.74 (sext, J ¼ 7:2 Hz, 1H), 4.35 (sext,
J ¼ 7:2 Hz, 1H), 3.92 (m, 1H), 2.94 (m, 1H), 2.60 (m, 1H),
2.46 (m, 1H), 1.96 (m, 1H), 1.87 (m, 1H), 1.69 (d,
J ¼ 1:7 Hz, 3H), 1.66 (d, J ¼ 1:7 Hz, 3H), 1.56 (m, 4H),
1.46 (m, 3H), 0.99 (d, J ¼ 1:7 Hz, 3H), 0.93 (d, J ¼ 1:7 Hz,
3H), 0.83 (m, 1H), 0.80 (m, 1H). 13C NMR (75.4 MHz)
147.1, 139.3, 128.7–126.3, 68.5 (d, JCP ¼ 128:3 Hz), 64.2 (d,
JCP ¼ 8:0 Hz), 60.7 (d, JCP ¼ 4:6 Hz), 54.7 (d, JCP ¼ 5:7 Hz),
51.2, 39.6, 31.1 (d, JCP ¼ 10:3 Hz), 30.1 (d, JCP ¼ 6:9 Hz),
24.9, 24.6 (d, JCP ¼ 13:7 Hz), 24.4, 23.8, 23.7, 21.1, 20.0 (d,
JCP ¼ 6:9 Hz). 31P NMR d ¼ 39:8. IR: 3261, 2952, 2867,
1170, 699 cmÀ1. Mass spectra (Mþ) calcd 455.2827, found
455.2835. X-ray structure: crystallized frompetroleum
ether/EtOAc. Colourless prism, 0.56 · 0.38 · 0.16 mm3,
C27H39N2O2P,
monoclinic,
C2,
a ¼ 23:905ð2Þ,
ꢂ
b ¼ 10:4523ð13Þ, c ¼ 10:6764ð8Þ A, b ¼ 96:477ð5Þꢁ, Z ¼ 4,
Z0 ¼ 1. Bruker P4 diffractometer using Mo Ka radiation
ꢂ
(k ¼ 0:71073 A), T ¼ 297ð1Þ K, 4484 reflections measured
up to 2h ¼ 52.5ꢁ, 4201 independent data (Rint ¼ 1:77%) for
290 refined parameters. The structure was solved and
refined using standard methods8 using nonabsorption-
corrected data. Final R indices: R1 ¼ 4:02% for 3281
reflections having Fo > 4rðFoÞ and wR2 ¼ 10:15% for all
data. Absolute configuration fromthe refinement of a
Flack parameter: x ¼ 0:02ð10Þ. The crystallographic data
have been deposited with the CCDC (number 226195).
(3aR,7aR)-[2-Oxo-1,3-bis[(S)-a-phenylethyl]-octahydro-
2k5-benzo[1,3,2]diazaphosphol-2-yl]-phenyl-methanol, 3g
major isomer. Colourless crystals, mp ¼ 192–194 ꢁC,
3. (a) Blazis, V. J.; Koeller, K. J.; Spilling, C. D. J. Org. Chem.
1995, 60, 931–940; (b) Bennani, Y. L.; Hanessian, S. Chem.
Rev. 1997, 97, 3161; (c) Molt, O.; Schrader, T. Synthesis
2002, 2633–2670.
4. Devitt, P. G.; Kee, T. P. Tetrahedron 1995, 51, 10987–
10996.
1
½a À 118:76 (c 1, CHCl3). H NMR (400 MHz) d: 7.63–
D
7.17, (m, 15H), 5.30 (dd, J ¼ 4:4 Hz, JCP ¼ 11:4 Hz, 1H),
4.69–4.66 (m, 1H), 4.35–4.31 (m, 1H), 3.66 (dd, J ¼ 5:5 Hz,
J ¼ 11:9 Hz, 1H), 2.8 (d, J ¼ 8:4 Hz, 2H), 1.6 (d,
J ¼ 7:0 Hz, 3H), 1.51 (d, J ¼ 7:3 Hz, 3H), 1.59–1.38 (m,
5H), 1.25–0.57 (m, 3H). 13C NMR (100 MHz) 144.5, 143.5
5. Anaya de Parrodi, C.; Moreno, G. E.; Quintero, L.;
Juaristi, E. Tetrahedron: Asymmetry 1998, 9, 2093–2099.
ꢀ
6. Moreno, G. E.; Quintero, L.; Bernes, S.; Anaya de Parrodi,
C. Acta Crystallogr., Sect. C, accepted for publication.
7. (3aS,7aS)-(Naphthalen-2-yl)-[2-oxo-1,3-bis-[(S)-a-phen-
ylethyl]-octahydro-2k5-benzo[1,3,2]diazaphosphol-2-yl]-
methanol, 3d major isomer. Colourless crystals, mp ¼ 192–
(d, JCP ¼ 6:2 Hz), 128.2–126.3, 72.6, 71.4, 61.3 (d JCP ¼
5:4 Hz), 60.8 (d, JCP ¼ 7:7 Hz), 53.3, 49.5 (d, JCP ¼ 5:4 Hz),
30.4 (d, JCP ¼ 6:2 Hz), 30.2 (d, JCP ¼ 9:3 Hz), 24.3, 19.2,
16.8. 31P NMR d ¼ 35:6. IR: 3423, 3238, 3059, 2940, 2867,