Synlett 2018; 29(02): 230-234
DOI: 10.1055/s-0036-1588579
letter
© Georg Thieme Verlag Stuttgart · New York

Study of the Cross-Metathesis Reaction of α-Hydroxy β,γ-Unsaturated Amides towards a Rapid and Flexible Total ­Synthesis of Symbioramide and its Isomer

Alexandre Gratais
CNRS, INSA, Université de Rouen, COBRA UMR 6014, 76183 Mont Saint Aignan Cedex, France   Email: [email protected]
,
Samir Bouzbouz*
CNRS, INSA, Université de Rouen, COBRA UMR 6014, 76183 Mont Saint Aignan Cedex, France   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 20 July 2017

Accepted after revision: 04 September 2017

Publication Date:
12 October 2017 (online)


Abstract

The reactivity of novel α-hydroxy β,γ-unsaturated amides in cross-metathesis reactions was extensively studied and used to perform a short total synthesis of symbioramide and its isomer from ­l-serine methyl ester.

Supporting Information

 
  • References and Notes

  • 1 Bouzbouz S. Synlett 2011; 1888
    • 2a Kobayashi J. Ishibashi M. Nakamura H. Hirata Y. Yamasu T. Sasaki T. Ohizumi Y. Experientia 1988; 44: 800
    • 2b Kobayashi J. J. Nat. Prod. 1989; 52: 225
    • 3a Nakagawa M. Yoshida J. Hino T. Chem. Lett. 1990; 1407
    • 3b Yoshida J. Nakagawa M. Seki H. Hino T. J. Chem. Soc., Perkin Trans. 1 1992; 343
  • 4 Azuma H. Takao R. Niiro H. Shikata K. Tamagaki S. Tachibana T. Ogino K. J. Org. Chem. 2003; 68: 2790
  • 5 Mori K. Uenishi K. Liebigs Ann. Chem. 1994; 41
  • 6 Takanami T. Tokoro H. Kato D. Nishiyama S. Sugai T. Tetrahedron Lett. 2005; 46: 3291
  • 7 Prevost S. Ayad T. Phansavath P. Ratovelomanana-Vidal V. Adv. Synth. Catal. 2011; 353: 3213
  • 8 Hess LC. Posner GH. Org. Lett. 2010; 12: 2120
    • 9a Schwab P. France MB. Ziller JW. Grubbs RH. Angew. Chem., Int. Ed. Engl. 1995; 34: 2039
    • 9b Schwab P. Grubbs RH. Ziller JW. J. Am. Chem. Soc. 1996; 118: 100
    • 9c Belderrain TR. Grubbs RH. Organometallics 1997; 16: 4001
    • 10a Kingsbury JS. Harrity JP. A. Bonitatebus PJ. Hoveyda AH. J. Am. Chem. Soc. 1999; 121: 791
    • 10b Harrity JP. A. Visser MS. Gleason JD. Hoveyda AH. J. Am. Chem. Soc. 1997; 119: 1488
    • 10c Harrity JP. A. La DS. Cefalo DR. Visser MS. Hoveyda AH. J. Am. Chem. Soc. 1998; 120: 2343
    • 11a Scholl M. Ding S. Lee CW. Grubbs RH. Org. Lett. 1999; 1: 953
    • 11b Chatterjee AK. Grubbs RH. Org. Lett. 1999; 1: 1751
    • 11c Chatterjee AK. Morgan JP. Scholl M. Grubbs RH. J. Am. Chem. Soc. 2000; 122: 3783
    • 12a Garber SB. Kingsbury JS. Gray BL. Hoveyda AH. J. Am. Chem. Soc. 2000; 122: 8168
    • 12b Gessler S. Randl S. Blechert S. Tetrahedron Lett. 2000; 41: 9973
    • 13a Neugnot B. Cintrat J.-C. Rousseau B. Tetrahedron 2004; 60: 3575
    • 13b Hong SH. Day MW. Grubbs RH. J. Am. Chem. Soc. 2004; 126: 7414
    • 13c Edlin CD. Faulkner J. Fengas D. Knight CK. Parker J. Preece I. Quayle P. Richards SN. Synlett 2005; 572
    • 13d Higman CS. Plais L. Fogg DE. ChemCatChem 2013; 5: 3548
    • 14a Fürstner A. Thiel OR. Lehmann CW. Organometallics 2002; 21: 331
    • 14b Feldman J. Murdzek JS. Davis WM. Schrock RR. Organometallics 1989; 8: 2260
  • 15 Chatterjee AK. Choi T.-L. Sanders D. Grubbs RH. Angew. Chem. 2001; 40: 1277

    • For examples of Lewis acids assisted cross-metathesis, see:
    • 16a Lübbe C. Dumrath A. Neumann H. Beller M. Kadyrov R. ChemCatChem 2014; 6: 105
    • 16b Nagarapu L. Gaikwad HK. Bantu R. Manikonda SR. Kumar CG. Pombala S. Tetrahedron Lett. 2012; 53: 1287
    • 16c Shafi S. Kędziorek M. Grela K. Synlett 2011; 124
    • 16d Penzer EB. Gadzikwa T. Nguyen ST. Org. Lett. 2008; 10: 5613
    • 16e Vedrenne E. Dupont H. Oualef S. Elkaïm L. Grimaud L. Synlett 2005; 670
  • 17 Chatterjee AK. Choi T.-L. Sanders D. Grubbs RH. J. Am. Chem. Soc. 2003; 125: 11360
  • 18 Representative Experimental Procedure and Characterization Data Compound 23: Allyltrimethylsilane (6.7 mL, 42 mmol, 3.0 equiv) was dissolved in dry CH2Cl2 (20 mL), then acryloyl chloride (1.12 mL, 14 mmol, 1.0 equiv), and HG(II) (219 mg, 2.5 mol%) were added. The reaction mixture was stirred at r.t. for 4 h. The obtained solution was slowly added to a solution of O-protected l -serine methyl ester 22 (5 g, 14 mmol, 1.0 equiv) in CH2Cl2 (15 mL) at –20 °C. i-Pr2EtN (4.86 mL, 28 mmol, 2.0 equiv) was then added to the solution and stirred for 1 h. After completion, the reaction was quenched with sat. aq NH4Cl solution and extracted with EtOAc (2 × 30 mL). The combined organic phases were washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (cyclohexane/EtOAc, 8:2) to give the corresponding product as a brown waxy solid 23 (5.84 g, 84%). Rf = 0.48 (cyclohexane/EtOAc, 8:2). [α]D 25 +24.0 (c 1.0, CHCl3). IR (neat): ν = 2953, 2858, 1747, 1661, 1627, 1504, 1428, 1248, 1111, 847, 701 cm–1.1H NMR (300 MHz, CDCl3): δ = 7.63–7.58 (m, 4 H), 7.43–7.35 (m, 6 H), 6.95 (dt, J = 15.1, 8.8 Hz, 1 H), 6.29 (d, J = 8.2 Hz, 1 H), 5.67 (d, J = 15.1 Hz, 1 H), 4.81 (dt, J = 8.1, 2.9 Hz, 1 H), 4.04 (ddd, J = 57.0, 10.2, 3.0 Hz, 2 H), 3.74 (s, 3 H), 1.72 (d, J = 8.8 Hz, 2 H), 1.04 (s, 9 H), 0.06 (s, 9 H). 13C NMR (75 MHz, CDCl3): δ = 170.6, 165.1, 143.0, 135.0, 134.9, 132.5, 132.3, 129.4, 129.4, 127.3, 120.8, 64.1, 53.7, 51.6, 26.2, 23.7, 18.8, –2.3. HRMS (ESI+): m/z calcd for C27H40NO4Si2 [M + H]+: 498.2496; found: 498.2500. Compound 25: Allylic alcohol 24 (2.64 g, 6 mmol, 1.0 equiv) was dissolved in dry CH2Cl2 (2 mL) with alkene (5.18 mL, 3.0 mmol, 3.0 equiv). Then HG(II) (94 mg, 2.5 mol%) was added, and the reaction mixture was stirred at r.t. for 24 h. The solution was concentrated under vacuum, and the residue was purified by silica gel column chromatography purified by column chromatography (CH2Cl2/EtOAc, 9:1). The product was obtained as a mixture of diastereoisomers; only the major isomer is described; colorless oil (1.79 g, 47%). Rf = 0.73 (CH2Cl2/EtOAc, 9:1). IR (neat): ν = 2924, 2954, 1751, 1659, 1520, 1112, 823, 701 cm–1.1H NMR (300 MHz, CDCl3): δ = 7.60–7.58 (m, 4 H), 7.43–7.36 (m, 6 H), 7.09 (d, J = 8.2 Hz, 1 H), 5.95 (dt, J = 15.3, 6.6 Hz, 1 H), 5.57 (dd, J = 15.4, 7.6 Hz, 1 H), 4.68 (dt, J = 8.3, 2.4 Hz, 1 H), 4.54 (d, J = 7.6 Hz, 1 H), 4.01 (ddd, J = 13.2, 10.1, 2.6 Hz, 2 H), 3.75 (s, 3 H), 3.25 (br s, 1 H), 2.05 (dt, J = 8.7, 6.8 Hz, 2 H), 1.41–1.26 (m, 24 H), 1.03 (s, 9 H), 0.88 (t, J = 6.6 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 172.3, 170.5, 137.0, 135.5, 135.5, 132.7, 132.6, 130.0, 127.9, 127.8, 127.1, 73.0, 64.2, 54.2, 52.5, 32.3, 32.0, 29.7, 29.7, 29.6, 29.5, 29.4, 29.3, 28.9, 26.7, 22.7, 19.3, 14.2. HRMS (ESI+): m/z calcd for C38H60NO5Si [M+H]+: 638.4241; found: 638.4236.