7360
X.-H. Xu et al. / Tetrahedron 64 (2008) 7353–7361
d
139.7, 128.6, 128.1, 127.4, 125.6 (q, JC–F¼284.3 Hz), 68.9 (q,
References and notes
JC–F¼28.5 Hz), 63.7, 54.1, 36.3, 25.3, 16.4, 11.6; 19F NMR (282 MHz,
ꢁ73.0 (d, J¼7.1 Hz, 3F); MS (ESI) m/z 276.1 (MþH)þ; IR (thin
1. (a) Knochel, P. Sci. Synth. 2004, 3, 5; (b) Nakamura, E. Organometallics in Syn-
thesis: A Manual; Schlosser, M., Ed.; Wiley: New York, NY, 2002; p 579; (c)
Fu¨ rstner, A. Organozinc Reagents; Knochel, P., Jones, P., Eds.; Oxford University
Press: New York, NY, 1999; p 287; (d) Erdik, E. Organozinc Reagents in Organic
Synthesis; CRC: Boca Raton, FL, 1996; (e) Knochel, P. Comprehensive Organic
Synthesis; Trost, B. M., Fleming, I., Shreiber, S. L., Eds.; Pergamon: Oxford, 1991;
Vol. 1, Chapter 1.7.
2. (a) Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H.
, Eds.; Springer: Berlin, 1999; (b) Noyori, R. Asymmetric Catalysis in Organic
Synthesis; Wiley: New York, NY, 1994; (c) Catalytic Asymmetric Synthesis; Ojima,
I., Ed.; VCH: New York, NY, 1993; (d) Principle and Application of Asymmetric
Synthesis; Lin, G.-Q., Li, Y.-M., Chan, A. S. C., Eds.; Wiley-Interscience, John Wiley
and Sons: New York, NY, 2001.
3. (a) Corey, E. J.; Sarshar, S.; Bordner, J. J. Am. Chem. Soc. 1992, 114, 7938; (b)
Fujimura, O.; Grubbs, R. H. J. Org. Chem. 1998, 63, 824; (c) Murakata, M.; Jono, T.;
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D. W.; Kim, S. H. Org. Lett. 2001, 3, 823; (g) Suri, J. T.; Vu, T.; Hernandez, A.;
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CDCl3)
d
film) 3362, 2967, 1456, 1269, 1163, 1103, 851, 701 cmꢁ1; HRMS calcd
for C14H21F3NO (MþH)þ: 276.1570. Found: 276.1579.
4.4.7. (2S,3S)-3-(Dibenzylamino)-1,1,1-trifluoro-4,4-dimethyl-2-
pentanol (18) and (2R,3S)-3-(dibenzylamino)-1,1,1-trifluoro-4,4-
dimethyl-2-pentanol (180)
By use of the same procedures as that described for 2b and 2b0,
compound 16 (5.468 g, 13.63 mmol) was converted to compounds
18 (2.628 g, 53% for four steps) and 180 (286 mg, 6% for four steps) as
26
clear oils. Compound 18: [
a]
ꢁ13.5 (c 1.04, CHCl3); 1H NMR
D
(300 MHz, CDCl3) d 7.31 (m, 10H), 4.53 (m, 1H), 3.77 (m, 4H), 2.75 (s,
1H), 2.34 (d, J¼6.3 Hz, 1H), 0.96 (s, 9H); 13C NMR (75.5 MHz, CDCl3)
d
139.3, 129.3, 128.2, 127.2, 125.5 (q, JC–F¼283.3 Hz), 70.5 (q, JC–F¼
30.9 Hz), 63.0, 56.9, 36.6, 29.2; 19F NMR (282 MHz, CDCl3)
d
ꢁ74.3 (d,
J¼9.3 Hz, 3F); MS (ESI) m/z 366.2 (MþH)þ, 388.1 (MþNa)þ; IR (thin
film) 3554, 2962,1455,1283,1141,1028, 852, 699 cmꢁ1; HRMS calcd
for C21H27F3NO (MþH)þ: 366.2039. Found: 366.2044. Compound
27
180: [
a]
ꢁ12.8 (c 0.80, CHCl3); 1H NMR (300 MHz, CDCl3)
d
7.28 (m,
4. McDaniel, D. H.; Brown, H. C. J. Org. Chem. 1958, 23, 420.
5. Charton, M. J. Am. Chem. Soc. 1969, 91, 615.
D
10H), 4.56 (s, 1H), 4.42 (m, 1H), 3.95 (m, 4H), 3.04 (d, J¼3.0 Hz, 1H),
6. (a) Reformatsky, S. Chem. Ber. 1887, 20, 1210; (b) Fu¨rstner, A. Synthesis 1989,
571; (c) Organozinc Reagent; Knochel, P., Philips, J., Eds.; Oxford University
Press: New York, NY, 1999; (d) Ocampo, R.; Dolbier, W. R., Jr. Tetrahedron 2004,
60, 9325; (e) Cozzi, P. G. Angew. Chem., Int. Ed. 2007, 46, 2568.
7. (a) Soai, K.; Kawase, Y. Tetrahedron: Asymmetry 1991, 2, 781; (b) Pini, D.;
Mastantuono, A.; Salvadori, P. Tetrahedron: Asymmetry 1994, 5, 1875; (c) Mas-
tatuono, A.; Pini, D.; Rolfini, C.; Salvadori, P. Chirality 1995, 7, 499; (d) Mi, A.;
Wang, Z.; Chen, Z.; Jiang, Y.; Chan, A. S. C.; Yang, T.-K. Tetrahedron: Asymmetry
1995, 6, 2641; (e) Andre´s, J. M.; Martin, Y.; Pedrosa, R.; Pe´rez-Encabo, A.
1.12 (s, 9H); 13C NMR (75.5 MHz, CDCl3)
125.7 (q, JC–F¼283.7 Hz), 68.7 (q, JC–F¼29.8 Hz), 63.2, 56.6, 37.8, 29.3;
d 138.8, 129.3, 128.4, 127.3,
19F NMR (282 MHz, CDCl3)
d
ꢁ75.0 (d, J¼9.9 Hz, 3F); MS (ESI) m/z
366.2 (MþH)þ, 388.2(MþNa)þ;IR (thin film)3444, 2960,1455,1282,
1163, 1029, 863, 699 cmꢁ1; HRMS calcd for C21H27F3NO (MþH)þ:
366.2039. Found: 366.2038.
´
´
Tetrahedron 1997, 53, 3787; (f) Andres, J. M.; Pedrosa, R.; Perez-Encabo, A.
Tetrahedron 2000, 56, 1217; (g) Ojida, A.; Yamano, T.; Taya, N.; Tasaka, A. Org.
Lett. 2002, 4, 3051; (h) Emmerson, D. P. G.; Hems, W. P.; Davis, B. G. Tetrahedron:
Asymmetry 2005, 16, 213; (i) Shin, E.-K.; Kim, H. J.; Kim, Y.; Kim, Y.; Park, Y. S.
Tetrahedron Lett. 2006, 47, 1933; (j) Kloetzing, R. J.; Thaler, T.; Knochel, P. Org.
Lett. 2006, 8, 1125.
4.4.8. (2S,3S)-3-Benzylamino-1,1,1-trifluoro-4,4-dimethyl-2-
pentanol (12d)
By use of the same procedures as that described for 12c, com-
pound 18 (1.480 g, 4.05 mmol) was converted to compound 12d
27
8. Andre´s, J. M.; Pedrosa, R.; Pe´rez-Encabo, A. Eur. J. Org. Chem. 2004, 1558.
9. Jiang, Y. Z.; Mi, A. Q.; Wang, Z. Y.; Li, S. J. Youji Huaxue 1994, 14, 68.
10. (a) Ruppert, I.; Schlich, K.; Volbach, W. Tetrahedron Lett. 1984, 25, 2195; (b)
Prakash, G. K. S.; Yudin, A. K. Chem. Rev. 1997, 97, 757.
11. (a) van der Zeijden, A. A. H. Tetrahedron: Asymmetry 1995, 6, 913; (b) Ishimaru,
K.; Tsuru, K.; Yabuta, K.; Wada, M.; Yamamoto, Y.; Akiba, K. Tetrahedron 1996, 52,
(580 mg, 52% for two steps) as a clear oil: [
1H NMR (300 MHz, CDCl3)
3.92 (m, 1H), 3.74 (d, J¼13.2 Hz, 1H), 3.65 (s, 1H), 2.66 (d, J¼5.1 Hz,
1H), 1.32 (s, 1H), 1.01 (s, 9H); 13C NMR (75.5 MHz, CDCl3)
140.3,
128.6, 128.1, 127.3, 125.6 (q, JC–F¼283.3 Hz), 70.4 (q, JC–F¼28.5 Hz),
a
]
þ24.5 (c 1.11, CHCl3);
D
d
7.25 (m, 5H), 4.01 (d, J¼13.2 Hz, 1H),
d
´
´
13137; (c) Andres, J. M.; de Elena, N.; Pedrosa, R.; Perez-Encabo, A. Tetrahedron
1999, 55, 14137; (d) Andre´s, J. M.; Pedrosa, R.; Pe´rez, A.; Pe´rez-Encabo, A.
Tetrahedron 2001, 57, 8521; (e) Andre´s, J. M.; Pedrosa, R.; Pe´rez-Encabo, A.;
Ramı´rez, M. Tetrahedron 2006, 62, 7783.
68.9, 55.6, 35.6, 27.6; 19F NMR (282 MHz, CDCl3)
d
ꢁ71.6 (d,
J¼6.8 Hz, 3F); MS (ESI) m/z 276.1 (MþH)þ, 298.1 (MþNa)+; IR (thin
film) 3429, 2962, 1455, 1262, 1164, 1074, 846, 700 cmꢁ1; HRMS
calcd for C14H21F3NO (MþH)þ: 276.1570. Found: 276.1567.
12. Hedenstro¨m, E.; Andersson, F.; Hjalmarsson, M. J. Chem. Soc., Perkin Trans. 1
2000, 1513.
13. Cohen, S. C.; Khedouri, E. J. Am. Chem. Soc. 1961, 83, 4228.
14. (a) Moser, H.; Rihs, G.; Sauter, H. Z. Z. Naturforsch., B. 1982, 37, 451; (b) Bloch, R.
Chem. Rev. 1998, 98, 1407; (c) Enders, D.; Reinhold, U. Tetrahedron: Asymmetry
1997, 8, 1895; (d) Johansson, A. Contemp. Org. Synth. 1995, 2, 393.
15. (a) Jacques, J.; Collet, A.; Wilen, S. H. Enantiomers, Racemates, and Resolution;
Wiley: New York, NY, 1981; (b) Whitesell, J. K. Chem. Rev. 1989, 89, 1581.
16. For review, see: Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069.
17. (a) Rozema, M. J.; Sidduri, A.; Knochel, P. J. Org. Chem. 1992, 57, 1956; (b)
Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117; (c) Vettel, S.; Vaupel, A.;
Knochel, P. Tetrahedron Lett. 1995, 36, 1023; (d) Vettel, S.; Vaupel, A.; Knochel, P.
J. Org. Chem. 1996, 61, 7473; (e) Langer, F.; Schwink, L.; Devasagayaraj, A.;
Chavant, P.-Y.; Knochel, P. J. Org. Chem. 1996, 61, 8229; (f) Micouin, L.; Knochel, P.
Synlett 1997, 327.
18. (a) Soai, K.; Hatanaka, T.; Miyazawa, T. J. Chem. Soc., Chem. Commun. 1992, 1097;
(b) Suzuki, T.; Narisada, N.; Shibata, T.; Soai, K. Tetrahedron: Asymmetry 1996, 7,
2519; (c) Andersson, P. G.; Guijarro, D.; Tanner, D. Synlett 1996, 727; (d) An-
dersson, P. G.; Guijarro, D.; Tanner, D. J. Org. Chem. 1997, 62, 7364; (e) Guijarro,
D.; Pinho, P.; Andersson, P. G. J. Org. Chem. 1998, 63, 2530; (f) Jimeno, C.; Vidal-
4.5. General procedure for the enantioselective addition of
diethylzinc to N-(diphenylphosphinoyl)imine
Phosphinoylimine 19 (46 mg, 0.15 mmol) and the ligand
(0.15 mmol) were dissolved in dry toluene (0.9 mL) under nitrogen,
and the mixture was stirred for 10 min at room temperature. To the
mixture was added Et2Zn in hexane (0.45 mL, 0.45 mmol) at room
temperature. After the mixture was stirred for 24 h, the reaction
was quenched with saturated aqueous ammonium chloride and the
aqueous layer was extracted with CH2Cl2. The combined organic
phase was washed with brine, dried over NaSO4, and concentrated
in vacuo. The residue was purified by silica gel flash column
chromatography (petroleum ether/ethyl acetate¼2:3) to give N-(1-
phenylpropyl)-P,P-diphenylphosphinoylamide 20 as a white solid.
The ee was determined HPLC analysis (Chiralpak OD column,
hexane/propan-2-ol¼90:10; flow rate 0.8 mL minꢁ1; rt, UV de-
tection at 214 nm).
`
Ferran, A.; Moyano, A.; Pericas, M. A.; Riera, A. Tetrahedron Lett. 1999, 40, 777;
(g) Brandt, P.; Hedberg, C.; Lawonn, K.; Pinho, P.; Andersson, P. G. Chem.dEur. J.
1999, 5, 1692; (h) Jimeno, C.; Reddy, K. S.; Sola`, L.; Moyano, A.; Perica`s, M. A.;
Riera, A. Org. Lett. 2000, 2, 3157; (i) Pinho, P.; Andersson, P. G. Tetrahedron 2001,
57, 1615; (j) Zhang, X.-M.; Gong, L.-Z.; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Choi, M. C.
K.; Chan, A. S. C. Tetrahedron Lett. 2001, 42, 6369; (k) Zhang, H.-L.; Zhang, X.-M.;
Gong, L.-Z.; Mi, A.-Q.; Cui, X.; Jiang, Y.-Z.; Choi, M. C. K.; Chan, A. S. C. Org. Lett.
2002, 4, 1399; (l) Beresford, K. J. M. Tetrahedron Lett. 2002, 43, 7175; (m) Zhang,
H.-L.; Jiang, F.; Zhang, X.-M.; Cui, X.; Gong, L.-Z.; Mi, A.-Q.; Jiang, Y.-Z.; Wu, Y.-D.
Chem.dEur. J. 2004, 10, 1481; (n) Beresford, K. J. M. Tetrahedron Lett. 2004, 45,
6041; (o) Almansa, R.; Guijarro, D.; Yus, M. Tetrahedron: Asymmetry 2007, 18,
896; (p) Almansa, R.; Guijarro, D.; Yus, M. Tetrahedron: Asymmetry 2007, 18,
2828; (q) El-Shehawy, A. A. Tetrahedron 2007, 63, 11754.
Acknowledgements
We thank the National Natural Science Foundation of China,
Ministry of Education of China and Shanghai Municipal Scientific
Committee for funding this work.