Download PDF
Synlett 2007(9): 1383-1386  
DOI: 10.1055/s-2007-980344
LETTER
© Georg Thieme Verlag Stuttgart · New York

Highly Stereoselective Cobalt-Catalyzed Allylation of Functionalized Diarylzinc Reagents

Guillaume Dunet, Paul Knochel*
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13, 81377 München, Germany
Fax: +49(89)218077680; e-Mail: Paul.Knochel@cup.uni-muenchen.de;
Further Information

Publication History

Received 27 February 2007
Publication Date:
23 May 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

Functionalized diarylzinc reagents react readily with ­allylic chlorides or phosphates in the presence of Co(acac)2 (10 mol%) to give the SN2 products in high yields and with retention of the double-bond configuration. Functionalities like ester, ketone, or cyano are tolerated.

Key words

catalysis - allylation - cobalt catalysis - organozinc reagents - stereoselective cross-coupling - nocarasin C

    References and Notes

  • 1a Tamao K. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pattenden G. Pergamon; Oxford: 1991.  Chap. 2.2.10.4.
    CrossrefGoogle Scholar
  • 1b Tsuji J. Palladium Reagents and Catalysts   Wiley; Chichester: 1995. 
    CrossrefGoogle Scholar
  • 1c Negishi E. Liu F. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002.  Chap. III.2.9.
    CrossrefGoogle Scholar
  • 1d Negishi E. Liao B. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002.  Chap. III.2.10.
    CrossrefGoogle Scholar
  • 1e Takahashi T. Kanno K. In Modern Organonickel Chemistry   Tamaru Y. Wiley-VCH; Weinheim: 2005.  Chap. 2.3.
    CrossrefGoogle Scholar
  • 1f Shintani R. Hayashi T. In Modern Organonickel Chemistry   Tamaru Y. Wiley-VCH; Weinheim: 2005.  Chap. 9.2.
    CrossrefGoogle Scholar
  • 1g Magid RM. Tetrahedron  1980,  36:  1901 
    CrossrefGoogle Scholar
  • 1h Lipshutz BH. Sengupta S. Org. React. (N.Y.)  1992,  41:  135 
    CrossrefGoogle Scholar
  • 1i Karlström ASE. Bäckvall J.-E. In Modern Organocopper Chemistry   Krause N. Wiley-VCH; Weinheim: 2002.  p.259 
    CrossrefGoogle Scholar
  • 1j Yorimitsu H. Oshima K. Angew. Chem. Int. Ed.  2005,  44:  4435 
    CrossrefGoogle Scholar
  • 2a Mizutani K. Yorimitsu H. Oshima K. Chem. Lett.  2004,  7:  832 
    CrossrefGoogle Scholar
  • 2b Gomes P. Gosmini C. Périchon J. J. Org. Chem.  2003,  68:  1142 
    CrossrefGoogle Scholar
  • 2c Gomes P. Gosmini C. Périchon J. Org. Lett.  2003,  5:  1043 
    CrossrefGoogle Scholar
  • 2d Yasui H. Mizutani K. Yorimitsu H. Oshima K. Tetrahedron  2006,  62:  1410 
    CrossrefGoogle Scholar
  • 2e For cobalt-catalyzed reactions involving organozinc reagents, see for example: Avedissian H. Berillon L. Cahiez G. Knochel P. Tetrahedron Lett.  1998,  39:  6163 
    CrossrefGoogle Scholar
  • 3 Reddy K. Knochel P. Angew. Chem., Int. Ed. Engl.  1996,  35:  1700 ; Angew. Chem. 1996, 108, 1812
    CrossrefGoogle Scholar
  • 4 Kneisel FF. Dochnahl M. Knochel P. Angew. Chem. Int. Ed.  2004,  43:  1017 
    CrossrefPubMedGoogle Scholar
  • 5 Recent review: Knochel P. Dohle W. Gommermann N. Kneisel FF. Kopp F. Korn T. Sapountzis I. Vu VA. Angew. Chem. Int. Ed.  2003,  42:  4302 
    CrossrefPubMedGoogle Scholar
  • For recent advances in halogen-magnesium exchange, see:
  • 6a Krasovskiy A. Knochel P. Angew. Chem. Int. Ed.  2004,  43:  3333 
    CrossrefPubMedGoogle Scholar
  • 6b Liu C.-Y. Knochel P. Org. Lett.  2005,  7:  2543 
    CrossrefPubMedGoogle Scholar
  • 6c Ren H. Krasovskiy A. Knochel P. Chem. Commun.  2005,  543 
    CrossrefPubMedGoogle Scholar
  • 6d Ren H. Krasovskiy A. Knochel P. Org. Lett.  2004,  6:  4215 
    CrossrefPubMedGoogle Scholar
  • 7 Prepared according to: Nowotny S. Tucker CE. Jubert C. Knochel P. J. Org. Chem.  1995,  60:  2762 
    Google Scholar
  • 8 Allylic phosphates are readily prepared from the corresponding allylic alcohols using diethyl chlorophosphate (1.05 equiv) and pyridine (2.2 equiv) in Et2O or CH2Cl2: Nowotny S. Tucker CE. Jubert C. Knochel P. J. Org. Chem.  1995,  60:  2762 
    Google Scholar
  • 9 Tsuda M. Nemoto A. Komaki H. Tanaka Y. Yazawa K. Mikami Y. Kobayashi J. J. Nat. Prod.  1999,  62:  1640 
    CrossrefGoogle Scholar
10

Representative Procedure for the Preparation of ( E )-Ethyl 4-(3,7-Dimethylocta-2,6-dienyl)benzoate (3b): In a dry nitrogen-flushed Schlenk tube equipped with a septum and a magnetic stirring bar, ethyl 4-iodobenzoate (718 mg, 2.60 mmol) and anhyd Li(acac) (35 mg) were dissolved in anhyd NMP (3.0 mL) and cooled to 0 °C. Then, i-Pr2Zn (0.27 mL, 5.9 M solution in Et2O, 1.59 mmol, 0.6 equiv) was added dropwise. The reaction mixture was stirred at room temperature until the exchange reaction was complete (12 h). In a dry nitrogen-flushed Schlenk tube equipped with a septum and a magnetic stirring bar, geranyl chloride (173 mg, 1 mmol) and Co(acac)2 (27 mg, 10 mol%) were dissolved in anhyd NMP (0.5 mL) and cooled to 0 °C. The freshly prepared diarylzinc reagent (1.3 mmol) was added dropwise. The reaction mixture was stirred at 0 °C, until the reaction was complete (GC monitoring). Saturated aq NH4Cl was added, and the mixture was extracted several times with Et2O. The organic layer was dried (MgSO4) and the volatiles were removed in vacuo (the mixture was heated to 50 °C while evaporating under high vacuum for 2 h). Purification by flash column chromatography (eluent: pentane-Et2O, 98:2) afforded 3b as a pale yellow oil (205 mg 72%). 1H NMR (400 MHz, CDCl3): δ = 7.88 (d, J = 8.2 Hz, 2 H), 7.16 (d, J = 8.6 Hz, 2 H), 5.22-5.27 (m, 1 H), 5.00-5.04 (m, 1 H), 4.28 (q, J = 7.0 Hz, 2 H), 3.33 (d, J = 7.4 Hz, 2 H), 1.96-2.07 (m, 4 H), 1.63 (d, J = 1.2 Hz, 3 H), 1.61 (d, J = 1.2 Hz, 3 H), 1.53 (s, 3 H), 1.31 (t, J = 7.0 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 165.7, 146.2, 136.1, 130.5, 128.6, 127.2, 127.0, 123.1, 121.0, 59.7, 38.6, 33.2, 25.5, 24.7, 16.7, 15.1, 13.3. IR (neat): 2968, 2913, 1711, 1605, 1442, 1366, 1252, 1174, 1101, 1029, 769 cm-1. MS (EI): m/z (%) = 286 (8), 243 (16), 241 (24), 218 (22), 189 (22), 145 (61), 143 (31), 123 (81), 69 (100). HRMS (EI): m/z calcd for C19H26O2: 286.1933; found: 286.1922. ( E )-3-(3,7-Dimethylocta-2,6-di-enyl)benzonitrile (3c): 1H NMR (300 MHz, CDCl3): δ = 7.24-7.42 (m, 4 H), 5.17-5.26 (m, 1 H), 4.96-5.05 (m, 1 H), 3.30 (d, J = 7.1 Hz, 2 H), 1.94-2.12 (m, 4 H), 1.62 (s, 3 H), 1.61 (s, 3 H), 1.53 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 142.2, 136.8, 131.9, 130.8, 130.7, 128.5, 128.0, 123.0, 120.3, 118.1, 111.3, 38.6, 32.7, 25.4, 24.7, 16.7, 15.2. IR (neat): 3379, 2968, 2924, 2230, 1600, 1582, 1482, 1434, 1379, 1096, 792 cm-1. MS (EI): m/z (%) = 239 (1), 196 (4), 171 (6), 156 (7), 123 (24), 69 (100). HRMS (EI): m/z calcd C17H21N: 239.1674; found: 239.1661. ( E )-1-(3,7-Dimethylocta-2,6-dienyl)-3-trifluoromethylbenzene (3d): 1H NMR (600 MHz, CDCl3): δ = 7.38-7.43 (m, 2 H), 7.31-7.37 (m, 2 H), 5.28-5.33 (m, 1 H), 5.06-5.11 (m, 1 H), 3.41 (d, J = 7.6 Hz, 2 H), 2.05-2.18 (m, 4 H), 1.72 (d, J = 1.0 Hz, 3 H), 1.68 (s, 3 H), 1.60 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 142.9, 137.5, 131.9, 131.8, 130.8 (q, J = 32.5 Hz), 128.9, 125.5 (q, J = 272.6 Hz), 125.2 (m), 124.2, 122.8 (m), 122.2, 39.9, 34.2, 26.7, 25.8, 17.9, 16.5. IR (neat): 2968, 2913, 1442, 1366, 1328, 1156, 1115, 824, 631 cm-1. MS (EI): m/z (%) = 282 (2), 239 (5), 159 (6), 123 (25), 69 (100). HRMS (EI): m/z calcd for C17H21F3: 282.1595; found: 282.1608. ( E )-1-Bromo-2-(3,7-dimethylocta-2,6-di-enyl)benzene (3e): 1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 7.4 Hz, 1 H), 7.21-7.24 (m, 2 H), 7.02-7.08 (m, 1 H), 5.27-5.33 (m, 1 H), 5.08-5.14 (m, 1 H), 3.45 (d, J = 7.4 Hz, 2 H), 2.04-2.17 (m, 4 H), 1.71 (d, J = 0.8 Hz, 3 H), 1.69 (d, J = 1.2 Hz, 3 H), 1.61 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 141.1, 137.5, 132.8, 131.8, 130.2, 127.6, 127.6, 124.9, 124.4, 121.5, 40.0, 34.8, 26.8, 26.0, 18.0, 16.5. IR (neat): 2968, 2913, 1604, 1500, 1442, 1366, 1101, 769 cm-1. MS (EI): m/z (%) = 294 (2), 292 (2), 251 (9), 249 (9), 145 (17), 144 (87), 143 (23), 129 (47), 128 (19), 123 (100), 69 (78). HRMS (EI): m/z calcd for C16H21Br: 292.0827; found: 292.0831. ( E )-1-(3,7-Dimethylocta-2,6-di-enyl)naphthalene (3f): 1H NMR (300 MHz, CDCl3): δ = 7.92-7.98 (m, 1 H), 7.73-7.80 (m, 1 H), 7.63 (d, J = 7.4 Hz, 1 H), 7.38-7.47 (m, 2 H), 7.23-7.36 (m, 2 H), 5.30-5.38 (m, 1 H), 4.98-5.07 (m, 1 H), 3.71 (d, J = 6.7 Hz, 2 H), 1.95-2.11 (m, 4 H), 1.71 (d, J = 1.5 Hz, 3 H), 1.58 (s, 3 H), 1.51 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 138.0, 136.6, 134.1, 132.4, 131.7, 128.9, 126.8, 125.9, 125.9, 125.8, 125.7, 124.5, 124.3, 123.1, 40.0, 31.9, 26.9, 25.9, 18.0, 16.5. IR (neat): 3045, 2966, 2913, 2853, 1597, 1510, 1440, 1396, 1376, 790 cm-1. MS (EI): m/z (%) = 264 (37), 196 (18), 195 (98), 193 (33), 181 (24), 167 (45), 166 (42), 165 (99), 153 (100), 141 (59), 123 (85), 69 (51). HRMS (EI): m/z calcd for C20H24: 264.1878; found: 264.1886.