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Synlett

Volumn , Issue 6, 2009, Pages 913-916

Chemistry of lactam-derived vinyl phosphates: Stereoselective synthesis of (+)-fagomine

(5) Bartali, Laura a Scarpi, Dina a Guarna, Antonio a Prandi, Cristina b Occhiato, Ernesto G a

a UNIVERSITY OF FLORENCE (Italy)

b UNIVERSITY OF TURIN (Italy)

Author keywords

(+) fagomine; Carbonylation; Palladium; Piperidine alkaloids; Stereoselective hydroborations

Indexed keywords

ENAMINE; FAGOMINE; LACTAM DERIVATIVE; PALLADIUM; PHOSPHATE; VINYL DERIVATIVE;

ARTICLE; CARBONYLATION; CATALYSIS; CHEMICAL BOND; DRUG SYNTHESIS; HYDROBORATION; OXIDATION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 63849112560 PISSN: 09365214 EISSN: 14372096 Source Type: Journal
DOI: 10.1055/s-0028-1088202 Document Type: Article

Times cited : (24)

References (47)

1
- 0029014202
- Foti, C. J.; Comins, D. L. J. Org. Chem. 1995, 60, 2656.
- (1995) J. Org. Chem , vol.60 , pp. 2656
- Foti, C.J.¹ Comins, D.L.²

2
- 0000436139
- Nicolaou, K. C; Shi, G.-Q.; Namoto, K.; Bemal, F. Chem. Commun. 1998, 1757.
- (1998) Chem. Commun , pp. 1757
- Nicolaou, K.C.¹ Shi, G.-Q.² Namoto, K.³ Bemal, F.⁴

3
- 12344261809
- (a) Toyooka, N.; Nemoto, H.; Kawasaki, M.; Martin Garraffo, H.; Spande, T. F.; Daly, J. W. Tetrahedron 2005, 61, 1187.
- (2005) Tetrahedron , vol.61 , pp. 1187
- Toyooka, N.¹ Nemoto, H.² Kawasaki, M.³ Martin Garraffo, H.⁴ Spande, T.F.⁵ Daly, J.W.⁶

4
- 19544371931
- (b) Occhiato, E. G.; Prandi, C; Ferrali, A.; Guama, A. J. Org. Chem. 2005, 70, 4542.
- (2005) J. Org. Chem , vol.70 , pp. 4542
- Occhiato, E.G.¹ Prandi, C.² Ferrali, A.³ Guama, A.⁴

5
- 0037118336
- (c) Toyooka, N.; Fukutome, A.; Nemoto, H.; Daly, J. W.; Spande, T. F.; Garraffo, H. M.; Kaneko, T. Org. Lett. 2002, 4, 1715.
- (2002) Org. Lett , vol.4 , pp. 1715
- Toyooka, N.¹ Fukutome, A.² Nemoto, H.³ Daly, J.W.⁴ Spande, T.F.⁵ Garraffo, H.M.⁶ Kaneko, T.⁷

6
- 0034689879
- (d) Bamford, S. J.; Luker, T.; Speckamp, W. N.; Hiemstra, H. Org. Lett. 2000, 2, 1157.
- (2000) Org. Lett , vol.2 , pp. 1157
- Bamford, S.J.¹ Luker, T.² Speckamp, W.N.³ Hiemstra, H.⁴

7
- 0033515505
- (e) Toyooka, N.; Okumura, M.; Takahata, H. J. Org. Chem. 1999, 64, 2182.
- (1999) J. Org. Chem , vol.64 , pp. 2182
- Toyooka, N.¹ Okumura, M.² Takahata, H.³

8
- 0030961411
- (f) Luker, T.; Hiemstra, H.; Speckamp, W. N. J. Org. Chem. 1997, 62, 3592.
- (1997) J. Org. Chem , vol.62 , pp. 3592
- Luker, T.¹ Hiemstra, H.² Speckamp, W.N.³

9
- 0033609875
- (g) Toyooka, N.; Okumura, M.; Takahata, H.; Nemoto, H. Tetrahedron 1999, 55, 10673.
- (1999) Tetrahedron , vol.55 , pp. 10673
- Toyooka, N.¹ Okumura, M.² Takahata, H.³ Nemoto, H.⁴

10
- 0000167908
- (h) Luker, T.; Hiemstra, H.; Speckamp, W. N. J. Org. Chem. 1997, 62, 8131.
- (1997) J. Org. Chem , vol.62 , pp. 8131
- Luker, T.¹ Hiemstra, H.² Speckamp, W.N.³

11
- 38849090679
- Occhiato, E. G.; Scarpi, D.; Guarna, A. Eur. J. Org. Chem. 2008, 524.
- (2008) Eur. J. Org. Chem , pp. 524
- Occhiato, E.G.¹ Scarpi, D.² Guarna, A.³

12
- 84962406523
- Most recent papers: (a) Cavalli, A.; Pacetti, A.; Recanatini, M.; Prandi, C.; Scarpi, D.; Occhiato, E. G. Chem. Eur. J. 2008, 14, 9292.
- Most recent papers: (a) Cavalli, A.; Pacetti, A.; Recanatini, M.; Prandi, C.; Scarpi, D.; Occhiato, E. G. Chem. Eur. J. 2008, 14, 9292.

13
- 41149121790
- (b) Deagostino, A.; Larini, P.; Occhiato, E. G.; Pizzuto, L.; Prandi, C.; Venturello, P. J. Org. Chem. 2008, 73, 1941.
- (2008) J. Org. Chem , vol.73 , pp. 1941
- Deagostino, A.¹ Larini, P.² Occhiato, E.G.³ Pizzuto, L.⁴ Prandi, C.⁵ Venturello, P.⁶

14
- 34250663140
- (c) Bartali, L.; Guarna, A.; Larini, P.; Occhiato, E. G. Eur. J. Org. Chem. 2007, 2152.
- (2007) Eur. J. Org. Chem , pp. 2152
- Bartali, L.¹ Guarna, A.² Larini, P.³ Occhiato, E.G.⁴

15
- 34250353928
- (d) Bartali, L.; Larini, P.; Guarna, A.; Occhiato, E. G. Synthesis 2007, 1733.
- (2007) Synthesis , pp. 1733
- Bartali, L.¹ Larini, P.² Guarna, A.³ Occhiato, E.G.⁴

16
- 33644776518
- (e) Larini, P.; Guarna, A.; Occhiato, E. G. Org. Lett. 2006, 8, 781.
- (2006) Org. Lett , vol.8 , pp. 781
- Larini, P.¹ Guarna, A.² Occhiato, E.G.³

17
- 0024245410
- Molyneux, R. J.; Benson, M.; Wong, R. Y.; Tropea, J. H.; Elbein, A. D. J. Nat. Prod. 1988, 51, 1198.
- (1988) J. Nat. Prod , vol.51 , pp. 1198
- Molyneux, R.J.¹ Benson, M.² Wong, R.Y.³ Tropea, J.H.⁴ Elbein, A.D.⁵

18
- 0016148809
- Koyama, M.; Sakamura, S. Agric. Biol. Chem. 1974, 38, 1111.
- (1974) Agric. Biol. Chem , vol.38 , pp. 1111
- Koyama, M.¹ Sakamura, S.²

19
- 0031896786
- (a) Nojima, H.; Kimura, I.; Chen, F.-J.; Sugiura, Y.; Haruno, M.; Kato, A.; Asano, N. J. Nat. Prod. i1998, 61, 397.
- J. Nat. Prod , vol.61 , Issue.I1998 , pp. 397
- Nojima, H.¹ Kimura, I.² Chen, F.-J.³ Sugiura, Y.⁴ Haruno, M.⁵ Kato, A.⁶ Asano, N.⁷

20
- 0032425224
- (b) Taniguchi, S.; Asano, N.; Tomino, F.; Miwa, I. Harm. Metab. Res. 1998, 30, 679.
- (1998) Harm. Metab. Res , vol.30 , pp. 679
- Taniguchi, S.¹ Asano, N.² Tomino, F.³ Miwa, I.⁴

21
- 0030900733
- (c) Kato, A.; Asano, N.; Kizu, H.; Matsui, K.; Watson, A. A.; Nash, R. J. J. Nat. Prod. 1997, 60, 312.
- (1997) J. Nat. Prod , vol.60 , pp. 312
- Kato, A.¹ Asano, N.² Kizu, H.³ Matsui, K.⁴ Watson, A.A.⁵ Nash, R.J.⁶

22
- 0035925104
- Watson, A. A.; Fleet, G. W. J.; Asano, N.; Molyneux, R. J.; Nash, R. Phytochemistry 2001, 56, 265.
- (2001) Phytochemistry , vol.56 , pp. 265
- Watson, A.A.¹ Fleet, G.W.J.² Asano, N.³ Molyneux, R.J.⁴ Nash, R.⁵

23
- 58649086312
- (a) Kumari, N.; Reddy, B. G.; Vankar, Y. D. Eur. J. Org. Chem. 2009, 160.
- (2009) Eur. J. Org. Chem , pp. 160
- Kumari, N.¹ Reddy, B.G.² Vankar, Y.D.³

24
- 34247601597
- (b) Yokoyama, H.; Ejiri, H.; Miyazawa, M.; Yamaguchi, S.; Hirai, Y. Tetrahedron: Asymmetry 2007, 18, 852.
- (2007) Tetrahedron: Asymmetry , vol.18 , pp. 852
- Yokoyama, H.¹ Ejiri, H.² Miyazawa, M.³ Yamaguchi, S.⁴ Hirai, Y.⁵

25
- 63849152194
- (c) Castillo, J. A.; Calveras, J.; Casas, J.; Mitjans, M.; Vinardell, M. P.; Parella, T.; Inoue, T.; Sprenger, G. A.; Joglar, J.; Clapés, P. Org. Lett. 2006, 8, 6070.
- (2006) Org. Lett , vol.8 , pp. 6070
- Castillo, J.A.¹ Calveras, J.² Casas, J.³ Mitjans, M.⁴ Vinardell, M.P.⁵ Parella, T.⁶ Inoue, T.⁷ Sprenger, G.A.⁸ Joglar, J.⁹ Clapés, P.¹⁰

26
- 0242500286
- (d) Takahata, H.; Banba, Y.; Ouchi, H.; Nemoto, H.; Kato, A.; Adachi, I. J. Org. Chem. 2003, 68, 3603.
- (2003) J. Org. Chem , vol.68 , pp. 3603
- Takahata, H.¹ Banba, Y.² Ouchi, H.³ Nemoto, H.⁴ Kato, A.⁵ Adachi, I.⁶

27
- 0035902404
- (e) Takahata, H.; Banba, Y.; Cheimi, A.; Hideo, N.; Kato, A.; Adachi, I. Tetrahedron: Asymmetry 2001, 12, 817.
- (2001) Tetrahedron: Asymmetry , vol.12 , pp. 817
- Takahata, H.¹ Banba, Y.² Cheimi, A.³ Hideo, N.⁴ Kato, A.⁵ Adachi, I.⁶

28
- 0034897853
- (f) Desire, J.; Dransfield, P. J.; Gore, P. M.; Shipman, M. Synlett 2001, 1329.
- (2001) Synlett , pp. 1329
- Desire, J.¹ Dransfield, P.J.² Gore, P.M.³ Shipman, M.⁴

29
- 84885738128
- (g) Effenberger, F.; Null, V. Liebigs Ann. Chem. 1992, 1211.
- (1992) Liebigs Ann. Chem , pp. 1211
- Effenberger, F.¹ Null, V.²

30
- 0004409595
- (h) Pederson, R. L.; Wang, C.-H. Heterocycles 1989, 28, 477.
- (1989) Heterocycles , vol.28 , pp. 477
- Pederson, R.L.¹ Wang, C.-H.²

31
- 0024337552
- (i) von der Osten, C. H.; Sinskey, A. J.; Barbas, C. F.; Pederson, R. L.; Wang, Y.-F.; Wang, C.-H. J. Am. Chem. Soc. 1989, 111, 3924.
- (1989) J. Am. Chem. Soc , vol.111 , pp. 3924
- von der Osten, C.H.¹ Sinskey, A.J.² Barbas, C.F.³ Pederson, R.L.⁴ Wang, Y.-F.⁵ Wang, C.-H.⁶

32
- 0023093138
- (j) Fleet, G. W. J.; Fellows, L. E.; Smith, P. W. Tetrahedron 1987, 43, 979.
- (1987) Tetrahedron , vol.43 , pp. 979
- Fleet, G.W.J.¹ Fellows, L.E.² Smith, P.W.³

33
- 0021909642
- (k) Fleet, G. W. J.; Smith, P. W. Tetrahedron Lett. 1985, 26, 1469.
- (1985) Tetrahedron Lett , vol.26 , pp. 1469
- Fleet, G.W.J.¹ Smith, P.W.²

34
- 2942555626
- Recent progresses in the use of heterocyclicderived vinyl phoshpates: For a review see: a
- For a review see: (a) Occhiato, E. G. Mini-Rev. Org. Chem. 2004, 1, 149. Recent progresses in the use of heterocyclicderived vinyl phoshpates:
- (2004) Mini-Rev. Org. Chem , vol.1 , pp. 149
- Occhiato, E.G.¹

35
- 34250821664
- and references therein
- (b) Claveau, E.; Gillaizeau, I.; Blu, J.; Bruel, A.; Coudert, G. J. Org. Chem. 2007, 72, 4832; and references therein,
- (2007) J. Org. Chem , vol.72 , pp. 4832
- Claveau, E.¹ Gillaizeau, I.² Blu, J.³ Bruel, A.⁴ Coudert, G.⁵

36
- 0043076452
- (c) Lo Galbo, F.; Occhiato, E. G.; Guarna, A.; Faggi, C. J. Org. Chem. 2003, 68, 6360.
- (2003) J. Org. Chem , vol.68 , pp. 6360
- Lo Galbo, F.¹ Occhiato, E.G.² Guarna, A.³ Faggi, C.⁴

37
- 63849289918
- Typical Procedure To a solution of KHMDS (5.85 mL of a 0.5 M solution in toluene, 2.93 mmol) in THF (15.5 mL, cooled at-78 °C and under nitrogen atmosphere, was added a solution of 8 (687 mg, 2.34 mmol) in THF (6 mL) and the resulting mixture was stirred for 1.5 h. Afterward a solution of (PhO)2iP(O)Cl (605 μL, 2.93 mmol) in THF (5 mL) was added, stirring was continued for 1 h at -78 °C before allowing the temperature to rise to 0 °C. Then, a 10% NaOH aq soln (47 mL) was added, the mixture was extracted with Et2O (3 X 40 mL, washed with 10% NaOH (30 mL, and dried over anhyd K2CO3 for 30 min. After filtration and evaporation of the solvent (without heating and leaving a small of solvent, the crude phosphate was chromatographed (EtOAc-n-hexane, 1:2, 1% Et3N, Rf= 0.26) on a short layer of SiO 2 3.5 cm of SiO2 in a column with internal diameter of
- 4

38
- 63849266977
- We have already shown that generation of the enolate from a 4-silyloxy-substituted lactam causes both elimination of silanol (TBSOH) and migration of the silyl group to the enolate O atom. Thus, the phosphate has to be prepared from the lactam with a PMB-protected 4-OH group, see ref. 4
- 4.

39
- 63849165039
- 2.
- 2.

40
- 85022425406
- Oriyama, T.; Yatabe, K.; Kawada, Y.; Koga, G. Synlett 1995, 45.
- (1995) Synlett , pp. 45
- Oriyama, T.¹ Yatabe, K.² Kawada, Y.³ Koga, G.⁴

41
- 0028219945
- Momose, T.; Toyooka, N. J. Org. Chem. 1994, 59, 943.
- (1994) J. Org. Chem , vol.59 , pp. 943
- Momose, T.¹ Toyooka, N.²

42
- 63849102813
- Typical Procedure To a solution of 12 (266 mg, 0.81 mmol) in anhyd Et2O (23 mL, cooled at -78 °C, was added dropwise a solution of DIBAL-H (1.78 mL of a 1 M solution in n-hexane, 1.78 mmol) under stirring and nitrogen atmosphere. After 1 h, the reaction mixture was heated to 0 °C and left under stirring for 30 min. Then sat. aq NH4C1 (3.5 mL) was added, and the mixture was diluted with 11 mL of CH2C1 2. Then it was filtered through a Celite layer, the phases were separated, and the aqueous one was extracted with CH2C12 (3 X 20 mL, The combined organic extracts were dried over Na2SO 4, filtered, and concentrated. Chromatography (SiO2, eluant EtOAc-n-hexane 1:3, Rf= 0.25) afforded 13 (177 mg, in 73% yield as a colorless oil; [α]D20 +149.3 (c 0.35, CHC13, 1H NMR 400 MHz, CDC1
- 4Si: C, 55.78; H, 9.03; N, 4.65. Found: C, 55.44; H, 8.94; N, 4.39.

43
- 63849287361
- Compound 14. Chromatography (SiO2, eluant: EtOAc-n-hexane (1:12 then 1:6, Rf= 0.46; [α]D22+126.1 (c 0.49, CHC13, 1HNMR (400 MHz, CDC13, δ, 5.24 (d, J, 3.5 Hz, 1 H, 4.67 (s, 2 H, 4.50 (d, J, 13.1 Hz, 1 H, part of an AB system, 4.39 (d, J, 13.1 Hz, 1 H, part of an AB system, 4.19 (m, 1 H, 3.89 (ddd, J, 12.9, 5.5, 3.7 Hz, 1 H, 3.72 (s, 3 H, 3.66-3.60 (m, 2 H, 3.39 (ddd, J, 12.9, 9.2, 4.3 Hz, 1 H, 1.83-1.78 (m, 2 H, 0.96-0.92 (m, 2 H, 0.88 (s, 9 H, 0.08 (s, 3 H, 0.07 (s, 3 H, 0.02 (s, 9 H, 13C NMR (100 MHz, CDC13, 5, 154.2 (s, 137.0 (s, 115.0 (d, 93.9 (t, 68.0 (t, 65.3 (t, 62.7 (d, 52.8 (q, 41.5 (t, 33.2 (t, 25.9 (q, 3 C, 18.1 (s),18.0 (t, 1.4 (q, 3 C, 4.4 (q, 4.6 (q, MS: m/z, 431 (1, M, 228 (37, 73 100, Anal. Calcd for C20H 41NO
- 2: C, 55.64; H, 9.57; N, 3.24. Found: C, 55.31; H, 9.62; N, 3.02.

44
- 63849255921
- Typical Procedure To a solution of 14 (77 mg, 0.18 mmol) in anhyd THF (8.4 mL, under nitrogen atmosphere and cooled at -78 °C, was added a solution of BH3-THF (612 μL of a 1.0 M solution in THF, 0.612 mmol, After 5 min, the flask was submerged in an ice bath and left at 0 °C for 22 h. Then, under vigorous stirring, Me3NO (trimethylamine N-oxide, 162 mg, 2.16 mmol) was added and, after mounting a condenser, the reaction was heated at 65 °C (external bath) for 2 h. After cooling, EtOAc (16 mL) was added, the organic layer was washed with brine (2×8 mL) and dried over anhyd Na2SO4. Chromatography (EtOAc-n-hexane, 1:3, Rf= 0.22) afforded 15 (56 mg, 70, as a colorless oil; [α]D22 -1.4 (c 0.175, CHC13, 1H NMR (400 MHz, CDC13, δ, 4.65 (d, J, 6.6 Hz, 1 H, part of an AB system, 4.61 d, J, 6.6
- 2: C, 53.41; H, 9.64; N, 3.11. Found: C, 53.05; H, 9.32; N, 2.88.

45
- 63849199223
- The relative stereochemistry of 15 was assigned by NOES Y- 1D studies which also, together with the coupling constant values, showed that all substituents are axially oriented. There is no large trans-diaxial coupling constant between 2- H and 3-H, 3-H and 4-H, and between 4-H and either of the protons on C-5, as all of them are in equatorial position. Consistently, a strong NOE effect was found between axial 6-H and one of the protons (CH 2OSEM) on the side chain at C-2. In N-protected piperidines analogues to 15, the C-2 substituent is forced towards an axial orientation to relieve the A(1,3) strain with the N-protection. See: (a) Comins, D. L, Joseph, S. P. In Advances in Nitrogen Heterocycles, 2; Moody, C. J, Ed, JAI Press: Greenwich CT, 1996, 251-294
- (1,3) strain with the N-protection. See: (a) Comins, D. L.; Joseph, S. P. In Advances in Nitrogen Heterocycles, Vol. 2; Moody, C. J., Ed.; JAI Press: Greenwich CT, 1996, 251-294.

46
- 0000530296
- and ref. 3f
- (b) Ha, J. D.; Kang, C. H.; Belmore, K. A.; Cha, J. K. J. Org. Chem. 1998, 63, 3810; and ref. 3f.
- (1998) J. Org. Chem , vol.63 , pp. 3810
- Ha, J.D.¹ Kang, C.H.² Belmore, K.A.³ Cha, J.K.⁴

47
- 63849194534
- Typical Procedure A suspension of 15 (55 mg, 0.12 mmol) in 2 N HC1 (aq) was refluxed for 18 h. After cooling at r.t, it was washed with Et2O (5 × 10 mL, concentrated, and triturated with CHC1 3 to give 1-HC1 (22 mg, 100, as pale yellow solid after 12 h under vacuum; [α]D23+12.3 (c 0.38, H 2O);lit.10f[α]D20+12.9 (c 0.93, H2O, 1H NMR (400 MHz, D2O, δ, 3.97 (dd, J= 12.5, 3.1 Hz, 1 H, part of an ABX system, 3.91 (dd, J, 12.5, 5.1 Hz, 1 H, part of an ABX system, 3.75 (ddd, J= 14.0, 10.1, 4.7 Hz, 1 H, 3.56 (pseudo t, J= 10.1 Hz, 1 H, 3.48 (br d, J= 12.1 Hz, 1 H, 3.19-3.10 (m, 1 H+ 1 H, 2.27-2.22 (m, 1 H, 1.81-1.74 (m, 1 H, 13C NMR (100 MHz, D2O, δ, 70.9 (d, 70.1 (d, 60.9 (d, 58.2 (t, 42.4 (t, 29.1 t
- 2O): δ = 70.9 (d), 70.1 (d), 60.9 (d), 58.2 (t), 42.4 (t), 29.1 (t).

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