Palladium-Catalyzed Three-Component Coupling of Propargylic Oxiranes, Phenols and Carbon Dioxide

Abstract

(Z)-1-Phenoxyalkenyl-substituted cyclic carbonates have been produced from three-component coupling of propargylic oxiranes, phenols and carbon dioxide in the presence of palladium catalyst. The scope and limitations of this reaction have been ­examined by using various phenols and propargylic oxiranes. A plausible mechanism for the reaction is also proposed.

carbon dioxide - cyclic carbonates - epoxides - three-component coupling - palladium

References and Notes

1 Arakawa H. Aresta M. Armor JN. Barteau MA. Beckman EJ. Bell AT. Bercaw JE. Creutz C. Dinjus E. Dixon DA. Domen K. DuBois DL. Eckert J. Fujita E. Gibson DH. Goddard WA. Goodman DW. Keller J. Kubas GJ. Kung HH. Lyons JE. Manzer LE. Marks TJ. Morokuma K. Nicholas KM. Periana R. Que L. Rostrup-Nielson J. Sachtler WMH. Schmidt LD. Sen A. Somorjai GA. Stair PC. Stults BR. Chem. Rev.  2001,  101:  953 

For examples about palladium-catalyzed CO₂-fixation reactions to give cyclic carbonates, see:

2a Fujinami T. Suzuki T. Kamiya M. Fukuzawa S. Sakai S. Chem. Lett.  1985,  199 

2b Trost BM. Angle SR. J. Am. Chem. Soc.  1985,  107:  6123 

2c Trost BM. Lynch JK. Angle SR. Tetrahedron Lett.  1987,  28:  375 

2d Wershofen S. Scharf HD. Synthesis  1988,  854 

2e Suzuki S. Fujita Y. Kobayashi Y. Sato F. Tetrahedron Lett.  1989,  30:  3487 

2f Uemura K. Shiraishi D. Noziri M. Inoue Y. Bull. Chem. Soc. Jpn.  1999,  72:  1063 

2g Yoshida M. Ihara M. Angew. Chem. Int. Ed.  2001,  40:  616 

2h Yoshida M. Fujita M. Ishii T. Ihara M. J. Am. Chem. Soc.  2003,  125:  4874 

2i Yoshida M. Fujita M. Ihara M. Org. Lett.  2003,  5:  3325 

2j Yoshida M. Ohsawa Y. Ihara M. J. Org. Chem.  2004,  69:  1590 

2k Yoshida M. Ihara M. Chem. Eur. J.  2004,  2886 

2l Yoshida M. Ohsawa Y. Ihara M. Tetrahedron  2006,  62:  11218 

3a Yoshida M. Ueda H. Ihara M. Tetrahedron Lett.  2005,  46:  6705 

3b Yoshida M. Morishita Y. Ihara M. Tetrahedron Lett.  2005,  46:  3669 

4

General Procedure for the Palladium-Catalyzed Three-Component Coupling of Alkynylepoxides with Phenol and CO ₂ (Table 1, Entry 12).: To a stirred solution of alkynylepoxide 1a (32.9 mg, 166 µmol) in dioxane, were added p-cresol (20.8 µL, 199 µmol), Pd₂(dba)₃·CHCl₃ (8.6 mg, 8.3 µmol), dppp (13.7 mg, 33.2 µmol) and 3 Å MS (32.9 mg) at r.t., and stirring was continued for 20 h at 50 °C under CO₂ atmosphere. After filtration of the reaction mixture through a Celite pad followed by evaporation of the solvent, the residue was chromatographed on silica gel with hexane-EtOAc (96:4) as eluent to give the cyclic carbonate 3aa (40.9 mg, 70%) as colorless needles; mp 84-86 °C (from hexane-EtOAc). IR (neat): 2947, 1807, 1504 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.38 (d, J = 1.7 Hz, 2 H), 7.18-7.26 (m, 3 H), 6.97 (d, J = 8.8 Hz, 2 H), 6.81 (d, J = 8.8 Hz, 2 H), 6.58 (s, 1 H), 4.85 (dd, J = 5.1, 5.4 Hz, 1 H), 2.22 (s, 3 H), 2.13-2.19 (m, 1 H), 1.83-2.03 (m, 3 H), 1.60-1.66 (m, 3 H), 1.43-1.47 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 154.3, 153.1, 147.3, 132.7, 131.8, 130.2, 129.3, 128.3, 128.0, 117.3, 114.8, 84.1, 77.7, 30.2, 26.3, 20.4, 18.8, 17.7. MS: m/z = 350 [M⁺]. Anal. Calcd for C₂₂H₂₂O₄: C, 75.41; H, 6.35. Found: C, 75.35; H, 6.33.

5

Spectroscopic Data for 4a: colorless oil. IR (neat): 2947, 1809, 1491 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.32-7.47 (m, 5 H), 4.75 (dd, J = 5.12, 5.12 Hz, 1 H), 2.30-2.36 (m, 1 H), 2.11-2.18 (m, 1 H), 1.87-2.01 (m, 2 H), 1.72-1.78 (m, 1 H), 1.47-1.65 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 153.8, 131.9, 129.4, 128.4, 120.9, 88.3, 84.1, 80.2, 78.0, 34.2, 25.4, 20.0, 18.5. MS: m/z = 242 [M⁺]. HRMS: m/z [M⁺] calcd for C₁₅H₁₄O₃: 242.0943; found: 242.0952.

6 The effect of bidentate ligands on the formation of π-propargylpalladium complex has been examined: Tsutsumi K. Kawase T. Kakiuchi K. Ogoshi S. Okada Y. Kurosawa H. Bull. Chem. Soc. Jpn.  1999,  72:  2687 

7

In these reactions, trace amount of the corresponding (Z)-phenoxyalkenyl-substituted oxiranes (see ref. 3b) were obtained as byproducts.

It is known that chiral allenes can be synthesized from palladium-catalyzed reactions of chiral propargylic compounds via stereoselective anti-S_N2′ attack of palladium:

8a Elsevier CJ. Stehouwer PM. Westmijze H. Vermeer P. J. Org. Chem.  1983,  48:  1103 

8b Marshall JA. Adams ND. J. Org. Chem.  1997,  62:  367 

8c Dixneuf PH. Guyot T. Ness MD. Roberts SM. Chem. Commun.  1997,  2083 

8d Konno T. Tanikawa M. Ishihara T. Yamanaka H. Chem. Lett.  2000,  1360 

9 Mechanistic studies about formation of π-propargylmetal complex have been reported: Nishida T. Ogoshi S. Tsutsumi K. Fukunishi Y. Kurosawa H. Organometallics  2000,  19:  4488 

10a Casey CP. Nash JR. Yi CS. Selmeczy AD. Chung S. Powell DR. Hayashi RK. J. Am. Chem. Soc.  1998,  120:  722 

10b Ogoshi S. Kurosawa H. J. Synth. Org. Chem., Jpn.  2003,  61:  14 

For examples of palladium-catalyzed decarboxylative reaction of alkynyl-substituted cyclic carbonates, see:

11a Darcel C. Bartsch S. Bruneau C. Dixneuf PH. Synlett  1994,  457 

11b Darcel C. Bruneau C. Dixneuf PH. J. Chem. Soc., Chem. Commun.  1994,  1845 

11c Knight JG. Ainge SW. Baxtrer CA. Eastman TP. Harwood SJ. J. Chem. Soc., Perkin Trans. 1  2000,  3188