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Synlett 2003(8): 1207-1209
DOI: 10.1055/s-2003-39909
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Diene RCM in the Presence of a Protected Alkyne

Koji Ono, Toshiaki Nagata, Atsushi Nishida*
Graduate School of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba-shi, 263-8522, Japan
Fax: +81(43)2902909; e-Mail: nishida@p.chiba-u.ac.jp;
Further Information

Publication History

Received 13 April 2003
Publication Date:
11 June 2003 (online)

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Abstract

Diene RCM reactions with Grubbs catalyst proceed in the presence of a terminal alkyne protected by TMS or dicobalt hexacarbonyl complex, and this reaction was used to synthesize a key intermediate for nakadomarin A (2).

Key words

nakadomarin A - ring-crosing olefin metathesis (RCM) - enyne metathesis - Grubbs catalyst - dicobalt hexacarbonyl complex

    References

  • For recent reviews on metathesis, see:
  • 1a Armstrong SK. J. Chem. Soc., Perkin Trans. 1  1998,  371 
    CrossrefPubMedGoogle Scholar
  • 1b Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3013 
    CrossrefPubMedGoogle Scholar
  • 1c Trnka TM. Grubbs RH. Acc. Chem. Res.  2001,  34:  18 
    CrossrefPubMedGoogle Scholar
  • For recent reviews on enyne metathesis with ruthenium carbene complexes, see:
  • 2a Poulsen CS. Madsen R. Synthesis  2003,  1:  1 
    CrossrefGoogle Scholar
  • 2b For examples with other transition metals, see: Katz TJ. Sivavec TM. J. Am. Chem. Soc.  1985,  107:  737 
    CrossrefGoogle Scholar
  • 2c Trost BM. Tanoury GJ. J. Am. Chem. Soc.  1988,  110:  1636 
    CrossrefGoogle Scholar
  • 2d Barrett AGM. Baugh SPD. Braddock DC. Flack K. Gibson VC. Giles MR. Marshall EL. Procopiou PA. White AJP. Williams DJ. J. Org. Chem.  1998,  63:  7893 
    CrossrefGoogle Scholar
  • 2e See also: Trost BM. Doherty GA. J. Am. Chem. Soc.  2000,  122:  3801 
    CrossrefGoogle Scholar
  • 2f Fürstner A. Szillat H. Stelzer F. J. Am. Chem. Soc.  2000,  122:  6785 
    CrossrefGoogle Scholar
  • 2g See also: Fürstner A. Stelzer F. Szillat H. J. Am. Chem. Soc.  2001,  123:  11863 
    CrossrefGoogle Scholar
  • 2h Chatani N. Inoue H. Morimoto T. Muto T. Murai S. J. Org. Chem.  2001,  66:  4433 
    CrossrefGoogle Scholar
  • 3a Kitamura T. Sato Y. Mori M. Adv. Synth. Catal.  2002,  344:  678 
    CrossrefGoogle Scholar
  • 3b Kinoshita A. Sakakibara N. Mori M. Tetrahedron  1999,  55:  8155 
    CrossrefGoogle Scholar
  • 4a For an example of diene ring-closing metathesis with a tungsten catalyst in the presence of an alkyne, see: Kim S.-H. Zuercher WJ. Bowden NB. Grubbs RH. J. Org. Chem.  1996,  61:  1073 
    CrossrefGoogle Scholar
  • 4b For an example of olefin cross metathesis with Grubbs catalyst in the presence of an alkyne, see: Ratnayake AS. Hemscheidt T. Org. Lett.  2002,  4:  4667 
    CrossrefGoogle Scholar
  • 5 Synthesis of medium-rings by diene metathesis using substrates having an inner dicobalt hexacarbonyl complex using Grubbs first generation catalyst or molybdenum carbene catalyst has been reported very recently: Young DGJ. Burlison JA. Peters U. J. Org. Chem.  2003,  68:  3494 
    CrossrefGoogle Scholar
  • 6 Kobayashi J. Watanabe D. Kawasaki N. Tsuda M. J. Org. Chem.  1997,  62:  9236 
    CrossrefGoogle Scholar
  • 8 Scholl M. Ding S. Lee CW. Grubbs RH. Org. Lett.  1999,  1:  953 
    Google Scholar
  • 9 Under the forced conditions using 15 mol% of the catalyst, 3e gave 4e in 64% yield, and isomerization of vinylsilane to Z:E = 3:2 was observed. For an example of isomerization of olefin with second-generation Grubbs catalyst B, see: Lee CW. Grubbs RH. Org. Lett.  2000,  2:  2145 
    Google Scholar
  • 10a For a recent example of decomplexation into an alkyne, see: Jones GB. Wright JM. Rush TM. Plourde GWII. Kelton TF. Mathews JE. Huber RS. Davidson JP. J. Org. Chem.  1997,  62:  9379 
    Article in Thieme ConnectGoogle Scholar
  • 10b For an example of reductive decomplexation into an alkene, see: Takai S. Ploypradith P. Hamajima A. Kira K. Isobe M. Synlett  2002,  588 
    Article in Thieme ConnectGoogle Scholar
7

Nagata, T.; Nakagawa, M.; Nishida, A. J. Am. Chem. Soc. 2003, 125, in press.

11

A Typical Experimental Procedure for the Metathesis Reaction of 3c: Grubbs catalyst B (1.2 mg, 5 mol%) was added to a solution of 3c (20.4 mg, 28.7 mmol, Table [1] , entry 5) in CH2Cl2 29 mL (1 mmol) which was not degassed under a dry argon atmosphere. The resulting solution was placed in a 50 °C oil bath. After 1.5 h, the starting material 3c was completely converted to the cyclized product 4c on TLC. The solution was concentrated under reduced pressure and purified by flash chromatography on silica gel to give 4c (18.8 mg, 98%) as a red oil.

12

Spectral data for 4c and 7b. 2-(1-Phenylsulfonylamino-5-hexynyl)-5,10-dioxa-5,6,9,10-tetrahydrobenzocyclooctene-dicobalt hexacarbonyl complex (4c): IR (KBr): n = 3067, 2929, 2521, 2090, 2048, 2021, 1577, 1497, 1446, 1350, 1300, 1267, 1168, 1116, 1020, 999, 838, 739, 723 cm-1.
1H NMR (400 MHz, CDCl3): d = 1.55-1.68 (m, 4 H), 2.82 (t, J = 7.2 Hz, 2 H), 3.50 (t, J = 6.7 Hz, 2 H), 4.81 (d, J = 4.9 Hz, 2 H), 4.92 (d, J = 4.4 Hz, 2 H), 5.88 (dt, J = 11.0, 4.4 Hz, 1 H), 5.91 (dt, J = 11.0, 4.9 Hz, 1 H), 5.95 (s, 1 H), 6.59 (d, J = 2.7 Hz, 1 H), 6.68 (dd, J = 2.7, 8.5 Hz, 1 H), 6.87 (d, J = 8.5 Hz, 1 H), 7.46 (dd, J = 7.8, 7.8 Hz, 2 H), 7.57 (t, J = 7.8 Hz, 1 H), 7.60 (d, J = 7.8 Hz, 2 H). 13C NMR (100 MHz, CDCl3): d = 27.9, 28.4, 33.6, 50.3, 69.7, 70.7, 73.1, 96.6, 122.5, 122.9, 124.5, 127.7 (2 C), 128.7 (2 C), 128.9, 129.7, 132.6, 133.9, 138.1, 147.9, 148.0, 199.9 (6 C). LRMS (FAB): m/z = 684 [M + H]+. HRMS (FAB): Calcd for C28H24Co2NO10S [M + H]+ 683.9785. Found: 683.9781. (6aS,7aS,11aS,14bS)-13-(3-Butynyl)-9-(phenylsulfonyl)-3,4,6a,7,8,9,10,11,11a,14b-decahydrofuro[2¢¢3 ¢¢:3¢,4¢]pyri-do[3¢¢,4¢¢:1¢,5¢]cyclopenta[1¢,2¢:4,5]pyrrolo[1,2-a]azocin-1(2H)-one-dicobalt hexacarbonyl complex (7b): [a]23 D -38.8 (c 0.10, CHCl3). IR (neat): n = 3063, 2927, 2856, 2091, 2049, 2015, 1651, 1462, 1409, 1543, 1268, 1199, 1161, 1092, 981, 740, 691 cm-1 1H NMR (600 MHz, CDCl3): d = 1.43-1.52 (m, 1 H), 1.69-1.77 (m, 1 H), 1.99-2.09 (m, 4 H), 2.22-2.30 (m, 1 H), 2.33-2.37 (m, 2 H), 2.58-2.65 (m, 2 H), 2.92 (t, J = 7.4 Hz, 2 H), 2.98-3.01 (m, 1 H), 3.01 (d, J = 12.7 Hz, 1 H), 3.15-3.26 (m, 2 H), 3.29-3.33 (m, 1 H), 3.51 (d, J = 12.7 Hz, 1 H), 4.55-4.58 (m, 1 H), 5.09 (s, 1 H), 5.46 (d, J = 12.1 Hz, 1 H), 5.73-5.79 (m, 1 H), 5.90 (s, 1 H), 5.97 (s, 1 H), 7.52 (dd, J = 7.7, 8.1 Hz, 2 H), 7.60 (t, J = 7.7 Hz, 1 H), 7.75 (d, J = 8.1 Hz, 2 H). 13C NMR (150 MHz, CDCl3): d = 29.1, 30.9, 32.50, 32.55, 39.0, 43.08, 43.13, 49.7, 56.8, 59.7, 63.0, 73.4, 95.5, 103.4 (2 C), 127.4, 129.1 (2 C), 129.3 (2 C), 132.7, 133.8, 137.4, 155.5, 159.8, 173.3, 199.7 (6 C). LRMS (FAB): m/z = 777 [M + H]+. HRMS (FAB): Calcd for C34H31Co2N2O10S [M + H]+ 777.0339. Found: 777.0363.