SCOPUS 정보 검색 플랫폼

Synlett

Volumn , Issue 5, 2008, Pages 671-674

Synthetic studies directed toward kaitocephalin: A highly stereocontrolled route to the right-hand pyrrolidine core

(4) Takahashi, Keisuke a Haraguchi, Natsumi a Ishihara, Jun a Hatakeyama, Susumi a

a NAGASAKI UNIVERSITY (Japan)

Author keywords

Kaitocephalin; Natural products; Pyrrolidines; Ring closure; Tsuji Trost reaction

Indexed keywords

1,5 PENTANEDIOL; KAITOCEPHALIN; N METHYL DEXTRO ASPARTIC ACID RECEPTOR BLOCKING AGENT; PALLADIUM; PENTANE; PYRROLIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; DECOMPOSITION; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; HORNER WADSWORTH EMMONS REACTION; METHANOLYSIS; NUCLEAR OVERHAUSER EFFECT; OXIDATION; RACEMIZATION; STEREOCHEMISTRY; SYNTHESIS; WITTIG REACTION;

EID: 41349106605 PISSN: 09365214 EISSN: None Source Type: Journal
DOI: 10.1055/s-2008-1042801 Document Type: Article

Times cited : (20)

References (33)

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11
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13
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16
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17
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18
- 41349102127
- 2Et did not give 13b.
- 2Et did not give 13b.

19
- 41349108849
- The ee values of 14a (entry 2) and 14b (entries 7, 9, 11) were determined by HPLC analysis [Daicel Chiralcell OJ-H, hexane-i-PrOH (20:1)] of 26 and 27, respectively (Scheme 4). (Chemical Equation Presented)
- The ee values of 14a (entry 2) and 14b (entries 7, 9, 11) were determined by HPLC analysis [Daicel Chiralcell OJ-H, hexane-i-PrOH (20:1)] of 26 and 27, respectively (Scheme 4). (Chemical Equation Presented)

20
- 41349105678
- Reaction of 13a Giving 14a (Entry 2) To a solution of 13a (51 mg, 0.17 mmol) in THF (3.3 mL) was added (Ph3P)4Pd (10 mg, 0.0583 mmol) under an argon atmosphere, and the mixture was refluxed for 1 h. The reaction mixture was diluted with EtOAc, washed with H2O and brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography twice [SiO2 5 g, hexane-EtOAc (3:1, SiO2 5 g, PhH-EtOAc (10:1, to give 14a as a colorless oil (35 mg, 68, 76% ee, α]D24 +56.5 (c 0.66, CHCl3, 1H NMR (300 MHz, CDCl3, δ, 7.00 (d, J, 15.9 Hz, 1 H, 5.73 (d, J, 15.9 Hz, 1 H, 5.43 (d, J, 10.2 Hz, 1 H, 4.20 (q, J, 7.0 Hz, 2 H, 3.89 (t, J, 10.5 H, 1 H, 3.76 (d, J, 10.5 Hz, 1 H, 3.56 (br s, 1 H, 3.41 (br s, 1 H, 1.75 (m, 4 H, 1.58 (s, 9 H, 1.29 t, J
- +]: 299.1733; found: 299.1717.

21
- 41349116509
- Reaction of 13b Giving 14b (Entry 11) To a solution of 13b (8.8 g, 27.6 mmol) and Et3N (3.87 ml, 27.6 mmol) in DMF (276 mL) was added (Ph3P)4Pd (1.6 g, 1.38 mmol) under an argon atmosphere, and the mixture was stirred for 0.5 h at 70°C. The reaction mixture was diluted with Et2O, washed with H2O and brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography [SiO2 600 g, hexane-EtOAc (2:1, to give 14b as a colorless oil (7.6 g, 86, 91% ee, α] D26 +47.2 (c 0.96, CHCl3, αH NMR (300 MHz, CDCl3, δ, 7.32 (s, 5 H, 7.02 (d, J, 15.9 Hz, 1 H, 5.76 (d, J, 15.9 Hz, 1 H, 5.20 (s, 2 H, 4.96 (d, J, 10.8 Hz, 1 H, 3.98-3.77 (m, 2 H, 3.74 (s, 3 H, 3.67-3.44 (m, 2 H, 1.87-1.78 (m, 4 H, 13C NMR 75 MHz, CDCl3, δ, 166.3, 155.9
- +]: 319.1421; found: 319.1420.

22
- 31144472907
- The authentic samples were prepared from the known aldehyde (Scheme 5), see: Bittermann, H.; Gmeiner, P. J. Org. Chem. 2006, 71, 97. (Chemical Equation Presented)
- The authentic samples were prepared from the known aldehyde (Scheme 5), see: Bittermann, H.; Gmeiner, P. J. Org. Chem. 2006, 71, 97. (Chemical Equation Presented)

23
- 0030905433
- (a) Hirai, Y.; Watanabe, J.; Nozaki, T.; Yokoyama, T.; Yamaguchi, S. J. Org. Chem. 1997, 62, 776.
- (1997) J. Org. Chem , vol.62 , pp. 776
- Hirai, Y.¹ Watanabe, J.² Nozaki, T.³ Yokoyama, T.⁴ Yamaguchi, S.⁵

24
- 0034738041
- (b) Masaki, H.; Maeyama, J.; Kameda, K.; Esumi, T.; Iwabuchi, Y.; Hatakeyama, S. J. Am. Chem. Soc. 2000, 122, 5216.
- (2000) J. Am. Chem. Soc , vol.122 , pp. 5216
- Masaki, H.¹ Maeyama, J.² Kameda, K.³ Esumi, T.⁴ Iwabuchi, Y.⁵ Hatakeyama, S.⁶

25
- 41349115876
- Compound 20: [α]D27 +103.6 (c 0.87, CHCl3, 1H NMR (500 MHz, CDCl3, ca 2:3 mixture of rotamers, δ, 7.99 (d, J, 7.0 Hz, 2 H, 7.92 (d, J, 7.0 Hz, 2 H, 7.65 (m, 1 H, 7.38 (m, 5 H, 5.65 (d, J, 7.0 Hz, 0.6 H, 5.24 (d, J, 7.5 Hz, 0.4 H, 5.14 (s, 1 H, 5.14 (d, J, 11.0 Hz, 0.4 H, 4.96 (d, J, 11.0 Hz, 0.6 H, 4.81 (dd, J, 8.0 Hz, 0.6 H, 4.73 (dd, J, 8.0 Hz, 0.6 H, 4.46 (dd, J, 8.0 Hz, 0.4 H, 4.43 (m, 0.6 H, 4.30 (m, 0.4 H, 4.10 (m, 0.4 H, 3.73 (m, 1 H, 3.67 (m, 1 H, 2.75 (m, 1 H, 2.17 (m, 3 H, 13C NMR (75 MHz, CDCl3, δ, 180.0, 167.2, 154.4, 148.8, 135.8, 134.2, 131.2, 129.6, 129.1, 129.0, 128.9, 128.8, 128.5, 128.2, 128.0, 78.1, 71.3, 68.7, 67.6, 58.6, 47.7, 31.1, 24.5. FT-IR (film, 1835, 1738, 1565 cm-1. HRMS EI, m/z calcd for C24H22N2O
- +]: 450.1425; found: 450.1427.

26
- 0001021787
- Ishizuka, T.; Kunieda, T. Tetrahedron Lett. 1987, 28, 4185.
- (1987) Tetrahedron Lett , vol.28 , pp. 4185
- Ishizuka, T.¹ Kunieda, T.²

27
- 41349095860
- Compound 22: [α]D23 +32.0 (c 1.14, CHCl3, 1H NMR (400 MHz, CDCl3, δ, 4.18-4.12 (m, 1 H, 4.06 (d, J, 3.9 Hz, 1 H, 3.75 (dd, J, 10.4, 2.0 Hz, 1 H, 3.68 (br s, 1 H, 3.22-3.16 (m, 1 H, 2.93-2.89 (m, 1 H, 2.22-2.17 (m, 1 H, 1.90-1.74 (m, 3 H, 1.53 (s, 9 H) 0.92-0.83 (m, 18 H, 0.07-0.01 (m, 12 H, 13C NMR (75 MHz, CDCl3, δ, 176.8, 150.2, 83.1, 73.1, 72.1, 64.7, 59.8, 47.0, 29.3, 28.0, 25.7, 25.6, 17.9, 4.8, 5.4; FT-IR (film, 1754, 1719, 1489 cm-1. HRMS EI, m/z calcd for C25H50N2O 5Si2 [M, 514.3260; found: 528.3258
- +]: 514.3260; found: 528.3258.

28
- 0000465072
- (a) Murray, R. W.; Iyanar, K. J. Org. Chem. 1996, 61, 8099.
- (1996) J. Org. Chem , vol.61 , pp. 8099
- Murray, R.W.¹ Iyanar, K.²

29
- 0030581336
- (b) Goti, A.; Nannelli, L. Tetrahedron Lett. 1996, 37, 6025.
- (1996) Tetrahedron Lett , vol.37 , pp. 6025
- Goti, A.¹ Nannelli, L.²

30
- 41349089283
- Oxidation of 22 to 23 To a solution of urea·H 2O2 (1.54 g, 16.4 mmol) in MeOH (5 mL) was added MeReO3 (47 mg, 0.16 mmol) under an argon atmosphere, and the mixture was stirred at r.t. for 10 min. A solution of 22 (449 mg, 0.82 mmol) in MeOH (8 mL) and SiO2 (1.35 g) were added and the mixture was stirred at r.t. for 1.5 h. The reaction was quenched with sat. Na2S 2O3 and the reaction mixture was extracted with EtOAc. The extract was washed with H2O and brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by column chromatography [SiO2 20 g, hexane-EtOAc (3:2, to give 23 (350 mg, 81, as a colorless viscous oil, α]D23 +39.2 (c 1.01, CHCl3, 1H NMR (500 MHz, CDCl3, δ, 7.17 (s, 1 H, 5.33 (d, J, 7.0 Hz, 1 H, 4.37 d, J, 10.5 Hz, 1 H, 3
- +]: 528.3035; found: 528.3051.

31
- 41349086824
- Compound 24: [α]D23 +19.2 (c 1.05, CHCl3, 1H NMR (300 MHz, CDCl3, δ, 8.03 (d, J, 7.2 Hz, 2 H, 7.60 (t, J, 7.3 Hz, 1 H, 7.47 (t, J, 7.5 Hz, 2 H, 6.37 (br s, 1 H, 5.24 (d, J, 5.7 Hz, 1 H, 4.53 (dd, J, 11.6, 3.6 Hz, 1 H, 4.26 (dd, J, 12.0, 8.1 Hz, 1 H, 3.81 (m, 1 H, 3.79 (s, 3 H, 3.29-2.15 (m, 1 H, 3.10-2.92 (m, 1 H, 2.38-2.31 (m, 1 H, 1.92-1.79 (m, 3 H, 13C NMR (75 MHz, CDCl 3, δ, 179.4, 165.6, 155.4, 133.6, 129.7, 129.1, 128.6, 77.6, 69.6, 68.1, 56.0, 55.1, 47.7, 29.9, 26.5. FT-IR (neat, 3240, 2262, 2875, 1720, 1448 cm-1. HRMS EI, m/z calcd for C17H 20N2O6 [M, 348.1306; found: 348.1321
- +]: 348.1306; found: 348.1321.

32
- 41349088579
- Oxidation of 24 to 25 Compound 24 (139 mg, 0.40 mmol) was oxidized using urea-H2O2 (827 mg, 8.80 mmol, MeReO 3 (11 mg, 0.044 mmol, and SiO2 (580 mg) in MeOH (5 mL) in the same manner as described in ref. 22. Purification of crude product by column chromatography [SiO2 7 g, MeOH-EtOAc (0:1 to 1:10, gave 25 (92 mg, 64, as a colorless viscous oil: [α]D 23 +65.9 (c 0.83, CHCl3, 1H NMR (300 MHz, CDCl3, δ, 8.04 (d, J, 7.2 Hz, 2 H, 7.64 (t, J, 7.2 Hz, 1 H, 7.49 (t, J, 7.2 Hz, 2 H, 7.07 (s, 1 H, 6.95 (br s, 1 H, 5.99 (d, J, 3.9 Hz, 1 H, 4.79 (dd, J, 11.1, 4.8 Hz, 1 H, 4.48 (dd, J, 11.1, 4.8 Hz, 1 H, 4.04-3.96 (m, 1 H, 3.78 (s, 3 H, 2.97, 2.91 (m, 1 H, 2.69-2.61 (m, 1 H, 2.56-2.51 (m, 2 H, 13C NMR 75 MHz, CDCl3, δ, 170.4, 165.1, 155.2, 133.9, 129.8
- +]: 362.1104; found: 362.1114.

33
- 41349100869
- 3c,4a but the desired coupling products were obtained in <10% yield, respectively. To improve the yield, these coupling reactions are now being examined under various conditions.
- 3c,4a but the desired coupling products were obtained in <10% yield, respectively. To improve the yield, these coupling reactions are now being examined under various conditions.

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