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

doi:10.1055/s-2008-1077968

LETTER

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;

Abstract

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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

Full Text

References

References and Notes

For recent reviews of transition-metal-catalyzed [2+2+2] cycloadditions, see:

<A NAME="RU04708ST-1A">1a</A> 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

<A NAME="RU04708ST-1B">1b</A> Heller B. Hapke M. Chem. Soc. Rev. 2007, 36: 1085

<A NAME="RU04708ST-1C">1c</A> Chopade PR. Louie J. Adv. Synth. Catal. 2006, 348: 2307

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<A NAME="RU04708ST-1F">1f</A> Yamamoto Y. Curr. Org. Chem. 2005, 9: 503

<A NAME="RU04708ST-1G">1g</A> Robinson JE. In Modern Rhodium-Catalyzed Organic Reactions Evans PA. Wiley-VCH; Weinheim: 2005. p.129

<A NAME="RU04708ST-1H">1h</A> Varela JA. Saá C. Chem. Rev. 2003, 103: 3787

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<A NAME="RU04708ST-2A">2a</A> Harvey DF. Johnson BM. Ung CS. Vollhardt KPC. Synlett 1989, 15

<A NAME="RU04708ST-2B">2b</A> For the use of stoichiometric zirconacyclopentadienes, see: Gleiter R. Schehlmann V. Tetrahedron Lett. 1989, 30: 2893

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<A NAME="RU04708ST-3A">3a</A> Tsuda T. Kiyoi T. Miyane T. Saegusa T. J. Am. Chem. Soc. 1988, 110: 8570

<A NAME="RU04708ST-3B">3b</A> Tekavec TN. Louie J. Org. Lett. 2005, 7: 4037

<A NAME="RU04708ST-3C">3c</A> Tekavec TN. Louie J. J. Org. Chem. 2008, 73: 2641

<A NAME="RU04708ST-4">4</A> 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

<A NAME="RU04708ST-5">5</A> For Ru catalysis, see: Yamamoto Y. Takagishi H. Itoh K. J. Am. Chem. Soc. 2002, 124: 6844

<A NAME="RU04708ST-6">6</A> 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

<A NAME="RU04708ST-7">7</A> Bennacer B. Fujiwara M. Lee S.-Y. Ojima I. J. Am. Chem. Soc. 2005, 127: 17756

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For examples of carbonyl insertion into a Rh-C bond, see:

<A NAME="RU04708ST-9A">9a</A> Krug C. Hartwig JF. J. Am. Chem. Soc. 2002, 124: 1674

<A NAME="RU04708ST-9B">9b</A> Fujii T. Koike T. Mori A. Osakada K. Synlett 2002, 298

<A NAME="RU04708ST-10A">10a</A> Tanaka K. Otake Y. Wada A. Noguchi K. Hirano M. Org. Lett. 2007, 9: 2203

After our publication, a similar manuscript was published, see:

<A NAME="RU04708ST-10B">10b</A> Tsuchikama K. Yoshinami Y. Shibata T. Synlett 2007, 1395

<A NAME="RU04708ST-11">11</A> 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

<A NAME="RU04708ST-12A">12a</A> Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed. 2007, 46: 3951

<A NAME="RU04708ST-12B">12b</A> Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed. 2008, 47: 3410

For selected recent examples, see:

<A NAME="RU04708ST-13A">13a</A> Mandal T. Samanta S. Zhao C.-G. Org. Lett. 2007, 9: 943

<A NAME="RU04708ST-13B">13b</A> Samanta S. Zhao C.-G. J. Am. Chem. Soc. 2006, 128: 7442

<A NAME="RU04708ST-13C">13c</A> Demir AS. Reis O. Kayalar M. Eymur S. Reis B. Synlett 2006, 3329

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For examples, see:

<A NAME="RU04708ST-14A">14a</A> Yamashita M. Kojima M. Yoshida H. Ogata T. Inokawa S. Bull. Chem. Soc. Jpn. 1980, 53: 1625

<A NAME="RU04708ST-14B">14b</A> 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:

<A NAME="RU04708ST-15A">15a</A> Gakis N. Heimgartner H. Schmid H. Helv. Chim. Acta 1975, 58: 748

For hetero-Diels-Alder reactions involving α,β-unsaturated acyl phosphonates, see:

<A NAME="RU04708ST-15B">15b</A> Evans DA. Johnson JS. Olhava EJ. J. Am. Chem. Soc. 2000, 122: 1635

For our accounts of [2+2+2] cycloadditions catalyzed by a cationic rhodium(I)-BINAP-type bisphosphine complex, see:

<A NAME="RU04708ST-16A">16a</A> Tanaka K. Synlett 2007, 1977

<A NAME="RU04708ST-16B">16b</A> Tanaka K. Nishida G. Suda T. J. Synth. Org. Chem. Jpn. 2007, 65: 862

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.

<A NAME="RU04708ST-18">18</A> 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

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.