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Synlett 2008(13): 2017-2022  
DOI: 10.1055/s-2008-1077968
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Use of Acyl Phosphonates as a Coupling Partner for Rhodium-Catalyzed [2+2+2] Cycloaddition: Unexpected Dependence of the Reactivity on Structures of α,ω-Diynes

Ken Tanaka*, Rie Tanaka, Goushi Nishida, Masao Hirano
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Fax: +81(42)3887037; e-Mail: tanaka-k@cc.tuat.ac.jp;
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Received 2 May 2008
Publikationsdatum:
15. Juli 2008 (online)

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Abstract

A cationic rhodium(I)-H8-BINAP complex catalyzes a [2+2+2] cycloaddition of 1,6- and 1,7-diynes with acyl phosphonates in high yields with high regioselectivity. Interestingly, the reactivity of α,ω-diynes toward acyl phosphonates is highly dependent on their own structures.

Key words

acylphosphonates - alkynes - cycloaddition - H8-BINAP - rhodium

    References and Notes

  • For recent reviews of transition-metal-catalyzed [2+2+2] cycloadditions, see:
  • 1a Agenet N. Buisine O. Slowinski F. Gandon V. Aubert C. Malacria M. In Organic Reactions   Vol. 68:  Overman LE. John Wiley; Hoboken: 2007.  p.1 
    Suche in Google Scholar
  • 1b Heller B. Hapke M. Chem. Soc. Rev.  2007,  36:  1085 
    Suche in Google Scholar
  • 1c Chopade PR. Louie J. Adv. Synth. Catal.  2006,  348:  2307 
    Suche in Google Scholar
  • 1d Gandon V. Aubert C. Malacria M. Chem. Commun.  2006,  2209 
  • 1e Kotha S. Brahmachary E. Lahiri K. Eur. J. Org. Chem.  2005,  4741 
  • 1f Yamamoto Y. Curr. Org. Chem.  2005,  9:  503 
    Suche in Google Scholar
  • 1g Robinson JE. In Modern Rhodium-Catalyzed Organic Reactions   Evans PA. Wiley-VCH; Weinheim: 2005.  p.129 
  • 1h Varela JA. Saá C. Chem. Rev.  2003,  103:  3787 
    Suche in Google Scholar
  • For the use of stoichiometric cobalt reagents, see:
  • 2a Harvey DF. Johnson BM. Ung CS. Vollhardt KPC. Synlett  1989,  15 
  • 2b For the use of stoichiometric zirconacyclopentadienes, see: Gleiter R. Schehlmann V. Tetrahedron Lett.  1989,  30:  2893 
    Suche in Google Scholar
  • 2c Takahashi T. Li Y. Ito T. Xu F. Nakajima K. Liu Y. J. Am. Chem. Soc.  2002,  124:  1144 
    Suche in Google Scholar
  • For Ni catalysis, see:
  • 3a Tsuda T. Kiyoi T. Miyane T. Saegusa T. J. Am. Chem. Soc.  1988,  110:  8570 
    Suche in Google Scholar
  • 3b Tekavec TN. Louie J. Org. Lett.  2005,  7:  4037 
    Suche in Google Scholar
  • 3c Tekavec TN. Louie J. J. Org. Chem.  2008,  73:  2641 
    Suche in Google Scholar
  • 4 For Ni-catalyzed [4+2+2] cycloaddition of 1,6-diynes with cyclobutanones, see: Murakami M. Ashida S. Matsuda T. J. Am. Chem. Soc.  2006,  128:  2166 
    Suche in Google Scholar
  • 5 For Ru catalysis, see: Yamamoto Y. Takagishi H. Itoh K. J. Am. Chem. Soc.  2002,  124:  6844 
    CrossrefPubMedSuche in Google Scholar
  • 6 For Ru(II)-catalyzed hydrative cyclization and [4+2] cycloaddition of yne-enones, see: Trost BM. Brown RE. Toste FD. J. Am. Chem. Soc.  2000,  122:  5877 
    CrossrefSuche in Google Scholar
  • 7 Bennacer B. Fujiwara M. Lee S.-Y. Ojima I. J. Am. Chem. Soc.  2005,  127:  17756 
    CrossrefPubMedSuche in Google Scholar
  • 8 Kong JR. Krische MJ. J. Am. Chem. Soc.  2006,  128:  16040 
    CrossrefSuche in Google Scholar
  • For examples of carbonyl insertion into a Rh-C bond, see:
  • 9a Krug C. Hartwig JF. J. Am. Chem. Soc.  2002,  124:  1674 
    Suche in Google Scholar
  • 9b Fujii T. Koike T. Mori A. Osakada K. Synlett  2002,  298 
  • 10a Tanaka K. Otake Y. Wada A. Noguchi K. Hirano M. Org. Lett.  2007,  9:  2203 
    Suche in Google Scholar
  • After our publication, a similar manuscript was published, see:
  • 10b Tsuchikama K. Yoshinami Y. Shibata T. Synlett  2007,  1395 
  • 11 Recently, we have reported a cationic rhodium(I)-H8-BINAP-catalyzed regio-, diastereo-, and enantioselective [2+2+2] cycloaddition of 1,6-enynes with electron-deficient ketones. See: Tanaka K. Otake Y. Sagae H. Noguchi K. Hirano M. Angew. Chem. Int. Ed.  2008,  47:  1312 
    Suche in Google Scholar
  • 12a Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed.  2007,  46:  3951 
    Suche in Google Scholar
  • 12b Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed.  2008,  47:  3410 
    Suche in Google Scholar
  • For selected recent examples, see:
  • 13a Mandal T. Samanta S. Zhao C.-G. Org. Lett.  2007,  9:  943 
    Suche in Google Scholar
  • 13b Samanta S. Zhao C.-G. J. Am. Chem. Soc.  2006,  128:  7442 
    Suche in Google Scholar
  • 13c Demir AS. Reis O. Kayalar M. Eymur S. Reis B. Synlett  2006,  3329 
  • 13d Kim DY. Wiemer DF. Tetrahedron Lett.  2003,  44:  2803 
    Suche in Google Scholar
  • For examples, see:
  • 14a Yamashita M. Kojima M. Yoshida H. Ogata T. Inokawa S. Bull. Chem. Soc. Jpn.  1980,  53:  1625 
    Suche in Google Scholar
  • 14b Kojima M. Yamashita M. Yoshida H. Ogata T. Synthesis  1979,  147 
  • To the best of our knowledge, only two examples of a cycloaddition reaction using acyl phosphonates as a coupling partner have been reported. For a photochemical cycloaddition with aziridines, see:
  • 15a Gakis N. Heimgartner H. Schmid H. Helv. Chim. Acta  1975,  58:  748 
    Suche in Google Scholar
  • For hetero-Diels-Alder reactions involving α,β-unsaturated acyl phosphonates, see:
  • 15b Evans DA. Johnson JS. Olhava EJ. J. Am. Chem. Soc.  2000,  122:  1635 
    Suche in Google Scholar
  • For our accounts of [2+2+2] cycloadditions catalyzed by a cationic rhodium(I)-BINAP-type bisphosphine complex, see:
  • 16a Tanaka K. Synlett  2007,  1977 
  • 16b Tanaka K. Nishida G. Suda T. J. Synth. Org. Chem. Jpn.  2007,  65:  862 
    Suche in Google Scholar
  • 18 Equilibrium coordination of the ester carbonyl oxygen vs. the alkyne moiety of a malonate-linked 1,6-diyne is proposed in the Ru-catalyzed [2+2+2] cycloaddition of alkynes, see: Yamamoto Y. Arakawa T. Ogawa R. Itoh K. J. Am. Chem. Soc.  2003,  125:  12143 
    Suche in Google Scholar
17

In general, terminal alkynes are more reactive and coordinative toward rhodium than internal alkynes. Therefore, the reaction of terminal 1,6-diyne 1d with 2b results in the rapid homo-[2+2+2] cycloaddition of 1d via a rhodacyclopentadiene intermediate. On the other hand, the formation of the rhodacyclopentadiene intermediate from terminal 1,7-diyne 1h may be slower than that from terminal 1,6-diynes for steric reasons. Thus, the reaction of 1h with 2b may furnish the oxarhodacyclopentene intermediate. Insertion of another terminal alkyne moiety of 1h followed by reductive elimination of rhodium furnishes the corresponding cross-[2+2+2] cycloaddition product 3hb in good yield.

19

Typical Procedure (Table 2, entry 1) Under an argon atmosphere, H8-BINAP (12.6 mg, 0.02 mmol) and [Rh(cod)2]BF4 (8.1 mg, 0.02 mmol) were dissolved in CH2Cl2 (2.0 mL), and the mixture was stirred at r.t. for 5 min. Hydrogen was introduced to the resulting solution in a Schlenk tube. After stirring at r.t. for 1 h, the resulting solution was concentrated to dryness and dissolved in CH2Cl2 (0.5 mL). To this solution was added dropwise over 1 min a solution of diyne 1a (55.1 mg, 0.20 mmol) and acyl phosphonate 2a (72.1 mg, 0.40 mmol) in CH2Cl2 (1.0 mL) at r.t. The mixture was stirred at r.t. for 1 h. The resulting solution was concentrated and purified by a preparative TLC (hexane-EtOAc, 1:1), which furnished 3aa (76.2 mg, 0.017 mmol, 84% yield) as a pale yellow oil.
Compound 3aa: IR (neat): 3052, 2983, 2867, 1661, 1347, 1237, 1164, 1022, 671 cm-¹. ¹H NMR (300 MHz, CDCl3): δ (E -isomer) = 7.74-7.63 (m, 2 H), 7.33-7.21 (m, 2 H), 4.49-4.19 (m, 4 H), 3.97-3.73 (m, 4 H), 2.37 (s, 3 H), 2.10 (s, 3 H), 1.90-1.77 (m, 6 H), 1.16 (t, J = 7.2 Hz, 6 H); δ (Z-isomer) = 7.74-7.63 (m, 2 H), 7.33-7.21 (m, 2 H), 4.30-4.19 (m, 4 H), 4.12-3.97 (m, 4 H), 2.38 (s, 3 H), 2.10 (s, 3 H), 1.90-1.77 (m, 3 H), 1.58 (dd, J = 13.5, 1.5 Hz, 3 H), 1.28 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 193.9, 149.6, 149.4, 143.6, 142.8, 142.7, 133.9, 131.6, 129.9, 129.7, 127.4, 126.4, 124.0, 61.64, 61.56, 58.87, 58.86, 55.2, 28.3, 27.9, 21.4, 20.0, 19.8, 16.2, 16.11, 16.10, 15.9, 15.8. ³¹P NMR (121 MHz, CDCl3): δ (E -isomer) = 17.8; δ (Z -isomer) = 17.9. ESI-HRMS: m/z calcd for C21H30NO6PSNa [M + Na]+: 478.1429; found: 478.1428.
Compound (E)-3ab: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 7.51 (d, J = 8.4 Hz, 2 H), 7.28 (d, J = 8.4 Hz, 2 H), 7.16-7.00 (m, 3 H), 6.95-6.83 (m, 2 H), 4.12-3.87 (m, 8 H), 2.45 (s, 3 H), 2.29 (d, J = 3.3 Hz, 3 H), 2.17 (s, 3 H), 1.18 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 193.3, 159.8, 148.7, 148.4, 147.6, 147.4, 143.7, 136.9, 133.1, 132.4, 131.8, 129.9, 128.22, 128.16, 127.91, 127.89, 127.62, 127.58, 127.3, 62.1, 62.0, 57.9, 54.8, 28.8, 21.5, 20.3, 20.2, 16.2, 16.1. ³¹P NMR (121 MHz, CDCl3): δ = 14.5.
Compound (Z)-3ab: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 7.76 (d, J = 8.4 Hz, 2 H), 7.41-7.24 (m, 5 H), 7.17-7.09 (m, 2 H), 4.52 (s, 2 H), 4.51-4.28 (m, 2 H), 3.92-3.67 (m, 2 H), 3.78-3.52 (m, 2 H), 2.40 (s, 3 H), 2.32 (s, 3 H), 1.68 (d, J = 2.7 Hz, 3 H), 1.04 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 193.9, 148.7, 148.6, 145.3, 145.2, 143.7, 136.0, 135.9, 134.0, 133.5, 132.04, 132.03, 131.1, 129.8, 128.83, 128.77, 128.53, 128.51, 127.83, 127.80, 127.5, 62.14, 62.06, 59.0, 55.3, 28.7, 21.5, 21.4, 21.2, 16.1, 16.0. ³¹P NMR (121 MHz, CDCl3): δ = 14.0.
Compound 3bb: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ (E -isomer) = 7.73 (d, J = 7.8 Hz, 2 H), 7.41-7.05 (m, 7 H), 4.60 (t, J = 4.2 Hz, 2 H), 4.37 (t, J = 4.2 Hz, 2 H), 3.91-3.77 (m, 2 H), 3.77-3.60 (m, 2 H), 3.36 (d, J = 0.9 Hz, 3H), 2.43 (s, 3 H), 2.38 (s, 3 H), 1.05 (t, J = 7.2 Hz, 6 H); δ (Z -isomer) = 7.57 (d, J = 7.5 Hz, 2 H), 7.41-7.05 (m, 5 H), 6.99 (d, J = 7.2 Hz, 2 H), 4.23 (t, J = 4.2 Hz, 2 H), 4.13-3.91 (m, 6 H), 3.82 (s, 3 H), 2.43 (s, 3 H), 2.22 (s, 3 H), 1.19 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 194.1, 193.7, 165.3, 164.8, 164.5, 143.7, 143.6, 141.0, 140.6, 140.5, 140.4, 140.3 138.7, 138.6, 138.5, 138.41, 138.38, 136.2, 136.0, 134.9, 134.8, 133.8, 133.7, 133.0, 129.8, 129.7, 128.6, 128.52, 128.49, 128.45, 128.22, 128.17, 127.9, 127.8, 127.6, 127.5, 127.4, 63.0, 62.9, 62.8, 59.88, 59.86, 59.3, 55.5, 55.3, 53.1, 52.5, 29.0, 28.8, 21.42, 21.38, 16.1, 16.0, 15.9. ³¹P NMR (121 MHz, CDCl3): δ (E -isomer) = 11.9; δ (Z -isomer) = 11.0.
Compound (E)-3ca: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 7.73 (d, J = 8.1 Hz, 2 H), 7.35 (d, J = 8.1 Hz, 2 H), 7.29-7.16 (m, 1 H), 4.46-4.35 (m, 4 H), 4.18-4.03 (m, 4 H), 2.44 (s, 3 H), 2.21 (s, 3 H), 1.85 (dd, J = 15.0, 1.5 Hz, 3 H), 1.33 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 194.0, 144.2, 141.7, 141.3, 135.5, 134.8, 133.2, 133.1, 132.9, 132.5, 130.0, 127.5, 62.3, 62.2, 57.8, 55.0, 29.9, 21.5, 16.4, 16.3, 14.9, 14.8. ³¹P NMR (121 MHz, CDCl3): δ = 19.3.
Compound (Z)-3ca: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 7.74 (d, J = 8.1 Hz, 2 H), 7.33 (d, J = 8.1 Hz, 2 H), 6.77-6.54 (m, 1 H), 4.51-4.43 (m, 2 H), 4.37-4.29 (m, 2 H), 4.07-3.90 (m, 4 H), 2.42 (s, 3 H), 2.20 (s, 3 H), 2.04 (dd, J = 13.2, 1.8 Hz, 3 H), 1.24 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 194.1, 143.9, 143.8, 143.7, 134.2, 134.0, 133.9, 133.6, 133.48, 133.47, 131.9, 129.8, 127.6, 62.1, 62.0, 59.1, 59.0, 55.0, 29.8, 22.1, 22.0, 21.5, 16.3, 16.2. ³¹P NMR (121 MHz, CDCl3): δ = 16.7.
Compound (E)-3eb: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 7.25-7.15 (m, 3 H), 7.07-6.97 (m, 2 H), 4.12-3.91 (m, 4 H), 3.60 (s, 6 H), 3.10-3.02 (m, 2 H), 2.95 (s, 2 H), 2.35 (d, J = 3.3 Hz, 3 H), 2.18 (s, 3 H), 1.20 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 195.4, 171.0, 152.0, 151.7, 151.6, 151.4, 137.4, 137.3, 133.8, 129.8, 128.8, 128.7, 127.8, 127.5, 127.3, 61.9, 61.8, 56.8, 53.0, 44.9, 40.8, 29.0, 20.2, 20.1, 16.2, 16.1. ³¹P NMR (121 MHz, CDCl3): δ = 15.6.
Compound (Z)-3eb: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 7.40-7.28 (m, 3 H), 7.22-7.16 (m, 2 H), 3.96-3.70 (m, 4 H), 3.74 (s, 6 H), 3.70-3.30 (m, 4 H), 2.33 (s, 3 H), 1.79 (d, J = 2.4 Hz, 3 H), 1.10 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 195.8 152.4, 152.2, 150.1, 150.0, 136.8, 136.6, 133.9, 130.5, 129.11, 129.05, 128.4, 128.0, 127.5, 127.4, 61.9, 61.8, 57.3, 53.0, 45.6, 41.0, 28.9, 21.1, 20.9, 16.1, 16.0. ³¹P NMR (121 MHz, CDCl3): δ = 14.7.
Compound (E)-3ha: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 9.66 (s, 1 H), 7.14-7.00 (m, 1 H), 4.20-3.95 (m, 4 H), 2.34-2.14 (m, 4 H), 1.77 (dd, J = 14.4, 1.8 Hz, 3 H), 1.75-1.59 (m, 4 H), 1.34 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 192.2, 154.0, 153.7, 140.9, 140.7, 135.6, 131.6, 129.2, 62.0, 61.9, 30.6, 21.7, 21.6, 21.2, 16.4, 16.3, 14.2, 14.1. ³¹P NMR (121 MHz, CDCl3): δ = 20.3.
Compound (Z)-3ha: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 9.79 (s, 1 H), 6.70-6.60 (m, 1 H), 4.12-3.92 (m, 4 H), 2.35-2.15 (m, 4 H), 2.04 (dd, J = 13.2, 1.8 Hz, 3 H), 1.74-1.56 (m, 4 H), 1.28 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 192.6, 155.6, 155.5, 141.0, 140.9, 135.1, 131.7, 129.3, 61.7, 61.6, 31.4, 21.8, 21.7, 21.6, 21.5, 21.1, 16.4, 16.3. ³¹P NMR (121 MHz, CDCl3): δ = 17.6.
Compound (E)-3hb: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 9.85 (s, 1 H), 7.54 (d, J = 23.1 Hz, 1 H), 7.32-7.13 (m, 5 H), 4.18-3.99 (m, 4 H), 2.16-2.00 (m, 4 H), 1.57-1.41 (m, 4 H), 1.26 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 191.6, 153.3, 153.0, 142.4, 142.2, 137.3, 135.9, 135.0, 134.4, 134.3, 128.6, 128.5, 128.4, 128.20, 128.17, 62.5, 62.4, 30.92, 30.90, 21.7, 21.0, 16.3, 16.2. ³¹P NMR (121 MHz, CDCl3): δ = 17.2.
Compound (Z)-3hb: pale yellow oil. ¹H NMR (300 MHz, CDCl3): δ = 9.93 (s, 1 H), 7.45-7.31 (m, 5 H), 7.08-6.88 (m, 1 H), 4.08-3.83 (m, 4 H), 2.50-2.38 (m, 2 H), 2.34-2.21 (m, 2 H), 1.75-1.64 (m, 4 H), 1.18 (t, J = 7.2 Hz, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 192.4, 155.5, 155.4, 144.4, 144.3, 138.5, 138.4, 137.7, 135.3, 135.17, 135.15, 128.3, 128.12, 128.05, 62.1, 62.0, 31.24, 31.21, 21.9, 21.7, 21.1, 16.2, 16.1. ³¹P NMR (121 MHz, CDCl3): δ = 15.1.