6502
G. Kumaraswamy, N. Jayaprakash / Tetrahedron Letters 51 (2010) 6500–6502
2745–2747; (d) Kumaraswamy, G.; Sadaiah, K.; Ramakrishna, D. S.; Naresh, P.;
Sridhar, B.; Jagadeesh, B. Chem. Commun. 2008, 5324–5326; (e) Kumaraswamy,
G.; Padmaja, M.; Markondaiah, B.; Jena, N.; Sridhar, B.; Udaya Kiran, M. J. Org.
Chem. 2006, 71, 337–340; (f) Kumaraswamy, G.; Padmaja, M. J. Org. Chem. 2008,
73, 5198–5201; (g) Kumaraswamy, G.; Markondaiah, B. Tetrahedron Lett. 2007,
48, 1707–1709; (h) Kumaraswamy, G.; Markondaiah, B. Tetrahedron Lett. 2008,
49, 327–330.
hydrochloride salt of 3 employing EDCI (1-ethyl-3-(3-dimethyl-
aminopropyl) carbodiimide) with HOBt (1-hydroxy-benzotriazole)
and Et3N. The coupled product 1 was isolated in 72% yield. The
spectral and analytical data of 1 were in full agreement with
reported data ½a D25
ꢀ
= ꢁ11.9 (c = 0.35, CHCl3). {lit.5
½
a 2D5
ꢀ
= ꢁ12.3
(c = 0.53, CHCl3)} (Scheme 3).
7. Trost, B. M.; Malhotra, S.; Fried, B. A. J. Am. Chem. Soc. 2009, 131, 1674–1675.
8. In place of ethyl diazoacetate, benzyl diazoacetate was employed. But, the
resulting product showed inferior enantioselectivity (er 87:13 by chiral HPLC,
Chiralpak AD–H column: 95/5 n-hexane/i-PrOH, flow rate 0.8 mL/min,
In conclusion, we have demonstrated a concise enantioselective
total synthesis of (2S,30R,70Z)-N-(30-hydroxy-70-tetradecenoyl)-
homoserine lactone, which was achieved using a catalytic asym-
k = 254 nm, smajor = 31.9 min, smajor = 34.7 min).
metric hydrogenation and
a prophenol–zinc-catalyzed diazo
9. Enders, D.; Vrettou, M. Synthesis 2006, 13, 2155–2158.
10. Boyle, P. H.; Davis, A. P.; Dempsey, K. J.; Hosken, G. D. Tetrahedron: Asymmetry
1995, 6, 2819–2828.
11. (a) Koch, T.; Buchardt, O. Synthesis 1993, 1065–1067; (b) Natelson, S.; Natelson,
E. A. Microchem. J. 1989, 40, 226–232; (c) Son, J.-K.; Woodard, R. W. J. Am. Chem.
Soc. 1989, 111, 1363–1367; (d) Baldwin, J. E.; North, M.; Flinn, A. Tetrahedron
1988, 44, 637–642; (e) Wang, M.-C.; Zhang, Q.-J.; Zhao, W.-X.; Wang, X.-D.;
Ding, X.; Jing, T.-T.; Song, M.-P. J. Org. Chem. 2008, 73, 168–176; (f) Seela, F.;
Cramer, F. Chem. Ber. 1976, 109, 82–89.
addition to imine reaction as genesis of chirality. Further, this route
will allow synthesizing all possible stereoisomers using an anti-
pode of C2-symmetric chiral template of corresponding ligands.
Acknowledgments
12. Sonnet, P. E. Org. Prep. Proced. Int. 1974, 6, 269–273.
13. Holmquist, C. R.; Roskamp, E. J. J. Org. Chem. 1989, 54, 3258–3260.
14. Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Nayori, R. J. Am. Chem. Soc. 1997, 119,
8738–8739.
15. Hamada, T.; Torii, T.; Izawa, K.; Nayori, R.; Ikariya, T. Org. Lett. 2002, 4, 4373–
4376.
We are grateful to Dr. J.S. Yadav, Director, IICT, for his constant
encouragement. The financial support was provided by the DST,
New Delhi, India (Grant No: SR/SI/OC-12/2007) and CSIR (New Del-
hi) is gratefully acknowledged for awarding the fellowship to N.J.
Thanks are also due to Dr. G.V.M. Sharma for his support.
16. Experimental details for key steps, Compound 10: To a solution of (S,S)-
prophenol (378 mg, 0.512 mmol) in anhydrous THF (6 mL) was added
a
solution of diethylzinc (1.0 mL of a 1 M solution in hexane) at 0 °C. The reaction
mixture was stirred at room temperature for 30 min. This solution was used as
catalyst solution for the below reaction. An oven dried two-neck round
bottomed flask was charged with activated 4 Å sieves, fitted with a septum,
evacuated, flame dried, and purged with nitrogen. The flask was cooled to room
temperature then furan-N-Boc-imine (2.0 g, 10.26 mmol) in THF (25 mL) and
the catalyst solution (0.125 M) were added successively. The resulting reaction
was cooled to 0 °C and ethyl diazoacetate (1.2 g, 10.26 mmol) was added
dropwise. The resulting solution was stirred for 12 h; after which time, the
reaction was then quenched with 0.5 M HCl (20 mL) and diluted with ethyl
acetate (30 mL). The contents were extracted with ethyl acetate (3 ꢂ 15 mL).
The combined organic phases were concentrated and the residue was purified
over silica column eluting with hexane/EtOAc = 95:5) to afford 1.96 g (62%) of
Supplementary data
Supplementary data (experimental procedures, spectral data
and copies of spectras for all compounds) associated with this arti-
References and notes
1. (a) Whitehead, N. A.; Barnard, A. M. L.; Slater, H.; Simpson, N. J. L.; Salmond, G.
P. C. FEMS Microbiol. Rev. 2001, 25, 365–404; (b) Schripsema, J.; de Rudder, K. E.
E.; van Vliet, T. B.; Lankhorst, P. P.; de Vroom, E.; Kijne, J. W.; van Brussel, A. A.
N. J. Bacteriol. 1996, 178, 366–371.
2. Fuqua, W. C.; Winans, S. C.; Greenberg, E. P. J. Bacteriol. 1994, 176, 269–275.
3. (a) Hirsch, P. R. J. Gen. Microbiol. 1979, 113, 219–228; (b) Gray, K. M.; Pearson, J.
P.; Downie, J. A.; Boboye, B. E. A.; Greenberg, E. P. J. J. Bacteriol. 1996, 178, 372–
376; (c) Lithgow, J. K.; Willkinson, A.; Handman, A.; Rodelas, B.; Wisniewski-
Dye, F.; Williams, P.; Downie, A. J. Mol. Microbiol. 2000, 37, 81–97; (d) Blosser-
Middleton, R. S.; Gray, K. M. J. Bacteriol. 2001, 183, 6771–6777.
4. (a) Cao, J.-G.; Meighen, E. A. J. Bacteriol. 1993, 175, 3856; (b) Chhabra, S. R.;
Harty, C.; Hooi, D. S. W.; Daykin, M.; Williams, P.; Telford, G.; Pritcchard, D. I.;
Bycroft, B. W. J. Med. Chem. 2003, 46, 97–104; (c) Chhabra, S. R.; Stead, P.;
Bainton, N. J.; Salmond, G. P. C.; Stewart, G. S. A. B.; Williams, P.; Bycroft, B. W. J.
Antibiot. 1993, 46, 441–454; (d) Janssens, J. C. A.; Metzger, K.; Daniels, R.;
Ptacek, D.; Verhoeven, T.; Habel, L. W.; Vanderleyden, J.; De Vos, D. E.; De
Keersmaecker, S. C. J. Appl. Environ. Microbiol. 2007, 73, 535–544; (e) Pomini, A.
M.; Manfio, G. P. M.; Arau´ jo, W. L.; Marsaioli, A. J. J. Agric. Food. Chem. 2005, 53,
10 as yellow oil. ½a D25
ꢀ
= ꢁ8.5 (c = 0.45, CHCl3). 1H NMR (300 MHz, CDCl3):
d = 7.33–7.36 (m, 1H, furan), 6.30–6.33 (m, 1H, furan), 6.26 (d, J = 3.1 Hz, 1H,
furan), 5.65 (d, J = 7.5 Hz, 1H, CHNH), 5.35 (br s, 1H, H–N), 4.22 (q, J = 6.8 Hz,
2H, CO2CH2CH3), 1.46 (s, 9H, C(CH3)3), 1.28 (t, J = 6.8 Hz, 3H, CH3) ppm. 13C
NMR (75 MHz, CDCl3): d = 154.6, 151.0, 142.4, 110.5, 106.9, 61.0, 45.9, 28.2,
14.3 ppm. IR (KBr):
t
= 3364, 2092, 1685, 1521, 1163, 750, 632 cmꢁ1 MS (ESI)
.
m/z: 332 (M+Na)+. HRMS: calcd for C14H19N3O5Na 332.1222; found 332.1232.
Compound 2: To a solution of 4 (500 mg, 1.86 mmol) in anhydrous EtOAc
(5 mL) under argon was added HCOOH:Et3N (2:5) mixture (0.25 mL) followed
by the addition of Ru-catalyst A (0.011 g, 0.019 mmol, 1 mol %) which was pre-
dissolved in CH2Cl2 (2 ꢂ 1 mL). The resulting reaction mixture was heated to
50 °C for 48 h. After cooling the reaction mixture to room temperature, it was
diluted with ethyl acetate (20 mL) and filtered through a pad of silica gel. The
filtrate was concentrated in vacuo and the residue was subjected to silica gel
flash column chromatography (5% EtOAc in hexane) to afford 298 mg (59%) of
compound 2 as colorless oil. ½a D25
ꢀ
ꢁ11.3 (c = 0.25, CHCl3). {lit.5 a 2D2
½ ꢀ ꢁ14.0 (c
0.85, CHCl3)}. 1H NMR (300 MHz, CDCl3): d = 5.25–5.38 (m, 2H, @CHCH2), 4.16
(q, J = 6.8 Hz, 2H, CO2CH2CH3), 3.89–3.99 (m, 1H, CHOH), 2.91 (br s, 1H, OH),
2.45 (dd, J = 2.9, 16.6 Hz, 1H, 2-CHH), 2.35 (dd, J = 2.9, 16.6 Hz, 1H, 2-CHH),
1.96–2.08 (m, 4H, 2 ꢂ CH2), 1.23–1.57 (m, 15H, 5 ꢂ CH2 and CH3), 0.89 (t,
J = 6.8 Hz, 3H, CH3) ppm. 13C NMR (75 MHz, CDCl3): d = 173.1, 130.5, 129.1,
67.9, 60.6, 41.3, 36.0, 31.7, 29.7, 29.0, 27.2, 26.9, 25.5, 22.6, 14.1, 14.0 ppm. IR
´
6262–6265; (f) Pomini, A. M.; Araujo, W. L.; Marsaioli, A. J. J. Chem. Ecol. 2006,
32, 1769–1778; (g) Pomini, A. M.; Paccola-Meirelles, L. D.; Marsaioli, A. J. J.
Agric. Food. Chem. 2007, 55, 1200–1204.
5. Yajima, A.; Brussel, A. N. V.; Schripsema, J.; Nukada, T.; Yabuta, G. Org. Lett.
2008, 10, 2047–2050.
6. (a) Kumaraswamy, G.; Ramakrishna, D.; Santhakumar, K. Tetrahedron:
Asymmetry 2010, 21, 544–548; (b) Kumaraswamy, G.; Ramakrishna, G.;
Naresh, P.; Sridhar, B.; Jagadeesh, B.; Sridhar, B. J. Org. Chem. 2009, 74, 8468–
8471; (c) Kumaraswamy, G.; Jayaprakash, N.; Sridhar, B. J. Org. Chem. 2010, 75,
(KBr):
t = 3466, 2930, 2852, 2715, 1735, 1459, 1405, 1369, 1300, 1089, 1015,
.
725 cmꢁ1 MS (ESI) m/z: 293 (M+Na)+. HRMS: Calcd for C16H30O3Na 293.2092;
found 293.2093.