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Synlett 2010(2): 227-230  
DOI: 10.1055/s-0029-1218574
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Carbon-Carbon Double-Bond Isomerization and Diels-Alder Reaction of Dimethyl 5-Methylene-4-isopropylidene-2-cycloheptene-1,1-dicarboxylate with Dienophiles

Ping Lua, Jinqiang Kuangb, Shengming Ma*a,b
a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Linglin Lu, Shanghai 200032, P. R. of China
Fax: +86(21)64167510; e-Mail: masm@mail.sioc.ac.cn;
b Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, P. R. of China
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Publication History

Received 8 October 2009
Publication Date:
11 December 2009 (online)

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Carbon-Carbon Double-Bond Isomerization and Diels-Alder Reaction of Dimethyl 5-Methylene-4-isopropylidene-2-cycloheptene-1,1-dicarboxylate with DienophilesSynlett 2010; 2010(02): e2-e2
DOI: 10.1055/s-0029-1219193

Abstract

Tricyclic compounds were obtained as a single diastereomer via carbon-carbon double-bond isomerization-Diels-Alder reaction of dimethyl 5-methylene-4-isopropylidene-2-cycloheptene-1,1-dicarboxylate with dienophiles under the catalysis of [RhCl(cod)2]2/dppe/AgOTf. Further experiments provided the proof of isomerization of carbon-carbon double bond. Meanwhile a sequential double Diels-Alder reaction took place without carbon-carbon double-bond isomerization when 4-phenyl-4H-1,2,4-triazole-3,5-dione used as a dienophile.

Key words

Diels-Alder reactions - isomerizations - rhodium - stereo­selectivity - carbocycles

    References and Notes

  • 1a Jacobsen EN. Pfaltz A. Yamamoto H. Comprehensive Asymmetric Catalysis   Vol. 1-3:  Springer; Berlin: 1999. 
    Google Scholar
  • 1b Yamamoto H. Lewis Acids in Organic Synthesis   Vol. 1-2:  Wiley-VCH; New York: 2000. 
    Google Scholar
  • 1c Kobayashi S. Jørgensen KA. Cycloaddition Reaction in Organic Synthesis   Wiley-VCH; New York: 2002. 
    Google Scholar
  • 1d Jørgensen KA. Angew. Chem. Int. Ed.  2000,  39:  3558 
    Google Scholar
  • 2 Jolly RS. Luedtke G. Sheehan D. Livinghouse T.
    J. Am. Chem. Soc.  1990,  112:  4965 
    Google Scholar
  • 3a Gilbertson ST. Hoge GS. Genov DG. J. Org. Chem.  1998,  63:  10077 
    Google Scholar
  • 3b Heath H. Wolfe B. Livinghouse T. Bae SK. Synthesis  2001,  2341 
    Google Scholar
  • 3c O’Mahony DJR. Belanger DB. Livinghouse T. Synlett  1998,  443 
    Google Scholar
  • 4 Aikawa K. Akutagawa S. Mikami K. J. Am. Chem. Soc.  2006,  128:  12648 
    CrossrefGoogle Scholar
  • 5 Shintani R. Sannohe Y. Tsuji T. Hayashi T. Angew. Chem. Int. Ed.  2007,  46:  7277 
    CrossrefGoogle Scholar
  • 6 Lu P. Ma S. Org. Lett.  2007,  9:  2095 
    Google Scholar
  • 7 Wang B. Cao P. Zhang X. Tetrahedron Lett.  2000,  41:  8041 
    CrossrefGoogle Scholar
  • 8a Tani K. Pure Appl. Chem.  1985,  57:  1845 ; and references cited therein
    Google Scholar
  • 8b Akutagawa S. In Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; New York: 1999.  Chap. 23.
    Google Scholar
  • 8c Fu GC. In Modern Rhodium-Catalyzed Organic Reactions   Evans PA. Wiley-VCH; Weinheim: 2002.  Chap. 2.
    Google Scholar
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Crystal Data for Compound 4a
C21H27NO6, MW = 389.44, monoclinic, Pc, final R indices
[I > 2σ(I)], R1 = 0.0549, wR2 = 0.1248, R indices (all data): R1 = 0.0633, wR2 = 0.1299, a = 13.7051 (13) Å, b = 11.8187 (11) Å, c = 12.9999 (12) Å, β = 103.869 (2)˚, V = 2044.3 (3) ų, T = 293 (2) K, Z = 4, reflections collected/unique: 11758/4448 (R int = 0.1361), number of observations [>2σ(I)] 3626, parameters, 531. Supplementary crystallographic data have been deposited at the Cambridge Crystallographic Data Centre: CCDC 635123.

10

Crystal Data for 4e
C23H25N3O6, MW = 439.46, triclinic, P-1, final R indices
[I > 2σ(I)], R1 = 0.0394, wR2 = 0.1111, R indices (all data): R1 = 0.0498, wR2 = 0.1212, a = 8.4388 (4) Å, b = 8.5666 (4) Å, c = 16.3077 (7) Å, α = 99.1060 (10)˚, β = 100.0250 (10)˚, γ = 105.3230 (10)˚, V = 1093.44 (9) ų, T = 296 (2) K, Z = 2. Reflections collected/unique: 12810/ 3839 (R int = 0.0204), number of observations [>2σ(I)] 3118, parameters, 289. Supplementary crystallographic data have been deposited at the Cambridge Crystallographic Data Centre: CCDC 750106.

11

Crystal Data for 7
C33H34Cl4N6O8 (M + 2CH2Cl2), MW = 784.46, monoclinic, P2 (1)/c, final R indices [I > 2σ(I)], R1 = 0.0827, wR2 = 0.2345, R indices (all data): R1 = 0.1191, wR2 = 0.2521, a = 15.8125 (15) Å, b = 11.7056 (11) Å, c = 19.5084 (18) Å, β = 93.543 (2)˚, V = 3604.0(6) ų, T = 293 (2) K, Z = 4. Reflections collected/unique: 18430/6687 (R int = 0.1120), number of observations [>2σ(I)] 3630, parameters, 464. Supplementary crystallographic data have been deposited at the Cambridge Crystallographic Data Centre: CCDC 738018.