Electrophilic Addition to 1-Cyclopropylallenes: A Highly Efficient and Stereoselective Method for the Preparation of 6-Substituted-1,3-hexadienes

Abstract

Electrophilic additions to 1-cyclopropylallenes were investigated, providing an efficient and stereoselective method for the synthesis of 6-substituted-1,3-hexadienes.

Key words

cyclopropyl - allene - 1,3-hexadiene - electrophilic addition - stereoselective

References and Notes

• Selected reviews about MCP:
• 1a Brandi A. Goti A. Chem. Rev.  1998,  98:  589 
• 1b Brandi A. Cicchi S. Cordero FM. Goti A. Chem. Rev.  2003,  103:  1213 
• 1c Nakamura I. Yamamoto Y. Adv. Synth. Catal.  2002,  344:  111 
• Selected recent articles about allenes:
• 2a Zhou C. Li J. Lv B. Fu C.-L. Ma S.-M. Org. Lett.  2008,  10:  581 
• 2b Deng Y.-Q. Yu Y.-H. Ma S.-M. J. Org. Chem.  2008,  73:  585 
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• 2d Jiang X.-F. Ma S.-M. Tetrahedron  2007,  63:  7589 
• 2e Lu P. Ma S.-M. Org. Lett.  2007,  9:  5319 
• 2f Lu Z. Chai G.-B. Ma S.-M. J. Am. Chem. Soc.  2007,  129:  14546 
• 2g Guo H. Ma S.-M. Synthesis  2007,  2731 
• 2h Ma S.-M. Chem. Rev.  2005,  105:  2829 
• 2i For a monograph on the chemistry of allenes, see: Krause N. Hashmi ASK. Modern Allene Chemistry   Wiley-VCH; Weinheim: 2004. 
• 2j For a recent review on the synthesis of allenes, see: Brummond KM. DeForrest JE. Synthesis  2007,  795 
• 3a Shi M. Xu B. Org. Lett.  2002,  4:  2145 
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• 3e Huang J.-W. Shi M. Tetrahedron  2004,  60:  2057 
• 3f Huang X. Yu L. Synlett  2005,  2953 
• 3g Yu L. Huang X. Synlett  2007,  1371 
• 3h Chen Y. Shi M. J. Org. Chem.  2004,  69:  426 
• 3i Huang J.-W. Shi M. Tetrahedron Lett.  2003,  44:  9343 
• 3j Shao L.-X. Huang J.-W. Shi M. Tetrahedron  2004,  60:  11895 
• 3k Zhou H.-W. Huang X. Chen W.-L. Synlett  2003,  2080 
• Selected articles about this kind of reactions:
• 4a Mueller WH. Butler PE. Griesbaum K. J. Org. Chem.  1967,  32:  2651 
• 4b Okuyama T. Ohashi K. Izawa K. Fueno T. J. Org. Chem.  1974,  39:  2255 
• 4c Hagen JP. Harris JJ. Lakin D. J. Org. Chem.  1987,  52:  782 
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• 5 For details, see: Brandsma L. Verkruijsse HD. Synthesis of Acetylenes, Allenes and Cumulenes   Elsevier; Amsterdam: 1981. 
• Selected recent articles about conjugated dienes:
• 6a Zhou C. Fu C.-L. Ma S.-M. Tetrahedron  2007,  63:  7612 
• 6b Shi M. Wang B.-Y. Huang J.-W. J. Org. Chem.  2005,  70:  5606 
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• 7 Yu L. Meng B. Huang X. Synlett  2007,  2919 
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8

Preparation of ( Z )-2,6-Diiodo-3-phenyl-1,3-hexadiene (11a); Typical Procedure 1-Phenyl-1-cyclopropylallene (3a, 0.3mmol) was first dissolved in CH₂Cl₂ (1 mL). Under a nitrogen-atmosphere protection, a solution of I₂ (0.3 mmol) in CH₂Cl₂ (5 mL) was slowly added. The reaction proceeded very rapidly and color of I₂ disappeared immediately. The reaction liquid was stirred for an extra 1 min. Then, the solvent was evaporated under vacuum and residue was separated by preparation TLC (eluent: PE) to give 11a in 85% yield. The other 2,6-diiodo-1,3-hexadienes were prepared in a similar way.

Selected Spectroscopic Data of 11a IR (film): 3055, 3024, 2956, 2923, 1602, 1444, 1235, 1171, 1104, 908, 762, 696 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.25-7.45 (m, 5 H), 6.24 (s, 1 H), 6.21 (s, 1 H), 5.83 (t, J = 7.2 Hz, 1 H), 3.26 (t, J = 7.2 Hz, 2 H), 2.86-2.91 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 3.6, 33.4, 102.6, 126.6, 127.4, 128.1, 128.5, 130.6, 137.4, 145.8. MS (EI, 70 eV): m/z (%) = 410 (13) [M⁺], 283 (100). HRMS (EI): m/z calcd for C₁₂H₁₂I₂: 409.9029; found: 409.9038.

9

Spectroscopic Data of Compound 12a IR (film): 3352, 2924, 2876, 1603, 1444, 1088, 1047, 907, 763, 697cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.26-7.44 (m, 5 H), 6.23 (s, 1 H), 6.21 (s, 1 H), 5.93 (t, J = 7.6 Hz, 1 H), 3.79 (t, J = 6.4 Hz, 2 H), 2.55-2.60 (m, 2 H), 1.60 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 33.4, 61.8, 103.1, 125.3, 126.5, 127.9, 128.4, 130.6, 137.6, 146.2. MS (EI, 70 eV): m/z (%) = 300 (10) [M⁺], 173 (44), 141 (100). HRMS (EI): m/z calcd for C₁₂H₁₃OI: 300.0011; found: 300.0019.

11

Preparation of ( E )-3-Phenyl-6-chloro-1,3-hexadiene (13c); Typical Procedure Under a nitrogen-atmosphere protection, 1-phenyl-1-cyclopropylallene (3a, 0.3 mmol) and NaCl (0.6 mmol) were dissolved in AcOH (1 mL). The mixture was stirred at 80 °C for 4 h. Then, the solvent was evaporated under vacuum and residue was separated by preparation TLC (eluent: PE) to give 13c in 75% yield. The other 6-halo-1,3-hexadienes could be prepared in the similar way.
Selected Spectroscopic Data of 13c IR (film): 3057, 3024, 2959, 1492, 1444, 990, 919, 767, 702 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.24-7.34 (m, 5 H), 6.77-6.82 (m, 1 H), 5.56 (t, J = 7.2 Hz, 1 H), 5.32 (d, J = 11.2 Hz, 1 H), 5.13 (d, J = 17.2 Hz, 1 H), 3.61 (t, J = 7.2 Hz, 2 H), 2.76-2.81 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 31.4, 43.9, 118.9, 127.2, 128.0, 128.7, 129.4, 132.7, 140.9, 142.4. MS (EI, 70 eV): m/z (%) = 192 (32) [M⁺], 143 (80), 128 (100). HRMS (EI): m/z calcd for C₁₂H₁₃Cl: 192.0706; found: 192.0712.

12

Spectroscopic Data of Compound 14a
E-Isomer: ¹H NMR (400 MHz, CDCl₃): δ = 7.13-7.39 (m, 5 H), 6.83-6.90 (m, 1 H), 5.59 (t, J = 7.2 Hz, 1 H), 5.28 (d, J =
11.2 Hz, 1 H), 5.10 (d, J = 17.2 Hz, 1 H), 3.50-3.59 (m, 4 H), 2.59-2.65 (m, 2 H), 1.24 (t, J = 7.2 Hz, 3 H).
Z-Isomer: ¹H NMR (400 MHz, CDCl₃): δ = 7.13-7.39 (m, 5 H), 6.54-6.61 (m, 1 H), 5.77 (t, J = 7.6 Hz, 1 H), 5.01 (d, J = 10.8 Hz, 1 H), 4.70 (d, J = 17.2 Hz, 1 H), 3.36-3.45 (m, 4 H), 2.21-2.26 (m, 2 H), 1.16 (t, J = 7.2 Hz, 3 H).
Mixture of Z- and E-isomers: IR (film): 2974, 2863, 1491, 1443, 1377, 1112, 911, 768, 703 cm^-1. MS (EI, 70 eV): m/z (%) = 202 (10) [M⁺], 201 (17), 156 (96), 129 (100). HRMS (EI): m/z calcd for C₁₄H₁₈O: 202.1358; found: 202.1356.