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

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2008(13): 2017-2022
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;

Further Information

Publication History

Received 2 May 2008
Publication Date:
15 July 2008 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

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

Google Scholar
1b Heller B. Hapke M. Chem. Soc. Rev. 2007, 36: 1085

Google Scholar
1c Chopade PR. Louie J. Adv. Synth. Catal. 2006, 348: 2307

Google Scholar
1d Gandon V. Aubert C. Malacria M. Chem. Commun. 2006, 2209

Google Scholar
1e Kotha S. Brahmachary E. Lahiri K. Eur. J. Org. Chem. 2005, 4741

Google Scholar
1f Yamamoto Y. Curr. Org. Chem. 2005, 9: 503

Google Scholar
1g Robinson JE. In Modern Rhodium-Catalyzed Organic Reactions Evans PA. Wiley-VCH; Weinheim: 2005. p.129

Google Scholar
1h Varela JA. Saá C. Chem. Rev. 2003, 103: 3787

Google Scholar
For the use of stoichiometric cobalt reagents, see:
2a Harvey DF. Johnson BM. Ung CS. Vollhardt KPC. Synlett 1989, 15

Google Scholar
2b For the use of stoichiometric zirconacyclopentadienes, see: Gleiter R. Schehlmann V. Tetrahedron Lett. 1989, 30: 2893

Google Scholar
2c Takahashi T. Li Y. Ito T. Xu F. Nakajima K. Liu Y. J. Am. Chem. Soc. 2002, 124: 1144

Google Scholar
For Ni catalysis, see:
3a Tsuda T. Kiyoi T. Miyane T. Saegusa T. J. Am. Chem. Soc. 1988, 110: 8570

Google Scholar
3b Tekavec TN. Louie J. Org. Lett. 2005, 7: 4037

Google Scholar
3c Tekavec TN. Louie J. J. Org. Chem. 2008, 73: 2641

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

Google Scholar
5 For Ru catalysis, see: Yamamoto Y. Takagishi H. Itoh K. J. Am. Chem. Soc. 2002, 124: 6844

Crossref PubMed 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

Crossref Google Scholar
7 Bennacer B. Fujiwara M. Lee S.-Y. Ojima I. J. Am. Chem. Soc. 2005, 127: 17756

Crossref PubMed Google Scholar
8 Kong JR. Krische MJ. J. Am. Chem. Soc. 2006, 128: 16040

Crossref 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

Google Scholar
9b Fujii T. Koike T. Mori A. Osakada K. Synlett 2002, 298

Google Scholar
10a Tanaka K. Otake Y. Wada A. Noguchi K. Hirano M. Org. Lett. 2007, 9: 2203

Google Scholar
After our publication, a similar manuscript was published, see:
10b Tsuchikama K. Yoshinami Y. Shibata T. Synlett 2007, 1395

Google Scholar
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

Google Scholar
12a Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed. 2007, 46: 3951

Google Scholar
12b Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed. 2008, 47: 3410

Google Scholar
For selected recent examples, see:
13a Mandal T. Samanta S. Zhao C.-G. Org. Lett. 2007, 9: 943

Google Scholar
13b Samanta S. Zhao C.-G. J. Am. Chem. Soc. 2006, 128: 7442

Google Scholar
13c Demir AS. Reis O. Kayalar M. Eymur S. Reis B. Synlett 2006, 3329

Google Scholar
13d Kim DY. Wiemer DF. Tetrahedron Lett. 2003, 44: 2803

Google Scholar
For examples, see:
14a Yamashita M. Kojima M. Yoshida H. Ogata T. Inokawa S. Bull. Chem. Soc. Jpn. 1980, 53: 1625

Google Scholar
14b Kojima M. Yamashita M. Yoshida H. Ogata T. Synthesis 1979, 147

Google Scholar
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

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

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

Google Scholar
16b Tanaka K. Nishida G. Suda T. J. Synth. Org. Chem. Jpn. 2007, 65: 862

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

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.