Copper(I)-Catalyzed C-C
and C-O Coupling Reactions Using Hydrazone ­Ligands

Takashi Mino; Fumitoshi Yagishita; Masanori Shibuya; Kenji Kajiwara; Hiroaki Shindo; Masami Sakamoto; Tsutomu Fujita

doi:10.1055/s-0029-1217822

LETTER

Copper(I)-Catalyzed C-C and C-O Coupling Reactions Using Hydrazone Ligands

Takashi Mino*, Fumitoshi Yagishita, Masanori Shibuya, Kenji Kajiwara, Hiroaki Shindo, Masami Sakamoto, Tsutomu Fujita
Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Fax: +81(43)2903401; e-Mail: tmino@faculty.chiba-u.jp;

Abstract

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Abstract

Copper-catalyzed C-C coupling reaction of aryl iodides with diethylmalonate in toluene at 90 ˚C gave arylated malonates using 5 mol% of CuI with hydrazone 1a as a ligand in good yields under an aerobic atmosphere. We also found CuI/hydrazone 1b in toluene to be an efficient catalytic system for C-O coupling reactions of aryl bromides with phenols to give aryl ethers in good yields at 110 ˚C under an aerobic atmosphere.

Key words

copper catalyst - hydrazone - C-C coupling - C-O coupling - malonate - aryl ether

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References and Notes

<A NAME="RU05809ST-1A">1a</A> Ley SV. Thomas AW. Angew. Chem. Int. Ed. 2003, 42: 5400

<A NAME="RU05809ST-1B">1b</A> Kunz K. Scholz U. Ganzer D. Synlett 2003, 2428

<A NAME="RU05809ST-1C">1c</A> Beletskaya IP. Cheprakov AV. Coord. Chem. Rev. 2004, 248: 2337

<A NAME="RU05809ST-2A">2a</A> Buchwald SL. Altman RA. J. Org. Chem. 2007, 72: 6190

<A NAME="RU05809ST-2B">2b</A> Lv X. Bao W. J. Org. Chem. 2007, 72: 3863

<A NAME="RU05809ST-2C">2c</A> Chen Y.-J. Chen H.-H. Org. Lett. 2006, 8: 5609

<A NAME="RU05809ST-2D">2d</A> Altman RA. Buchwald SL. Org. Lett. 2006, 8: 2779

<A NAME="RU05809ST-2E">2e</A> Guo X. Rao H. Fu H. Jiang Y. Zhao Y. Adv. Synth. Catal. 2006, 348: 2197

<A NAME="RU05809ST-2F">2f</A> Zhang H. Cai Q. Ma DW. J. Org. Chem. 2005, 70: 5164

<A NAME="RU05809ST-2G">2g</A> Buchwald SL. Antilla JC. Baskin JM. Barder TE. J. Org. Chem. 2004, 69: 5578

<A NAME="RU05809ST-2H">2h</A> Cristau H.-J. Cellier PP. Spindler J.-F. Taillefer M. Eur. J. Org. Chem. 2004, 695

<A NAME="RU05809ST-2I">2i</A> Ma D. Cai Q. Synlett 2004, 128

<A NAME="RU05809ST-2J">2j</A> Ma D. Cai Q. Zhang H. Org. Lett. 2003, 5: 2453

<A NAME="RU05809ST-2K">2k</A> Kwong FY. Buchwald SL. Org. Lett. 2003, 5: 793

<A NAME="RU05809ST-2L">2l</A> Antilla JC. Klapars A. Buchwald SL. J. Am. Chem. Soc. 2002, 124: 11684

<A NAME="RU05809ST-2M">2m</A> Buchwald SL. Klapars A. Huang XH. J. Am. Chem. Soc. 2002, 124: 7421

<A NAME="RU05809ST-2N">2n</A> Kwong FY. Klapars A. Buchwald SL. Org. Lett. 2002, 4: 581

<A NAME="RU05809ST-2O">2o</A> Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc. 2001, 123: 7727

<A NAME="RU05809ST-3A">3a</A> Yip SF. Cheung HY. Zho Z. Kwong FY. Org. Lett. 2007, 9: 3469

<A NAME="RU05809ST-3B">3b</A> Xie X. Cai G. Ma D. Org. Lett. 2005, 7: 4693

<A NAME="RU05809ST-3C">3c</A> Bate CG. Saejueng P. Verkataraman D. Org. Lett. 2004, 4: 1441

<A NAME="RU05809ST-3D">3d</A> Ma D. Liu F. Chem. Commun. 2004, 1934

<A NAME="RU05809ST-3E">3e</A> Zanon J. Klapars A. Buchwald SL. J. Am. Chem. Soc. 2003, 125: 2890

<A NAME="RU05809ST-3F">3f</A> Hennessy EJ. Buchwald SL. Org. Lett. 2002, 4: 269

<A NAME="RU05809ST-4A">4a</A> Nonappa PD. Pandurangan K. Maitra U. Wailes S. Org. Lett. 2007, 9: 2767

<A NAME="RU05809ST-4B">4b</A> Ma D. Cai Q. Xie X. Synlett 2005, 1767

<A NAME="RU05809ST-4C">4c</A> Cristau H.-J. Cellier PP. Hamada S. Spindler J.-F. Taillefer M. Org. Lett. 2004, 6: 913

<A NAME="RU05809ST-4D">4d</A> Wan Z. Jones CD. Koenig TM. Pu YJ. Mitchell D. Tetrahedron Lett. 2003, 44: 8257

<A NAME="RU05809ST-4E">4e</A> Nordmann G. Buchwald SL. J. Am. Chem. Soc. 2003, 125: 4978

<A NAME="RU05809ST-4F">4f</A> Ma D. Cai Q. Org. Lett. 2003, 5: 3799

<A NAME="RU05809ST-4G">4g</A> Buck E. Song ZJ. Tschaen D. Dormer PG. Volante RP. Reider PJ. Org. Lett. 2002, 4: 1623

<A NAME="RU05809ST-5">5</A> Mino T. Harada Y. Shindo H. Sakamoto M. Fujita T. Synlett 2008, 614

<A NAME="RU05809ST-6A">6a</A> Mino T. Shirae Y. Sakamoto M. Fujita T. Synlett 2003, 882

<A NAME="RU05809ST-6B">6b</A> Mino T. Shirae Y. Sakamoto M. Fujita T. J. Org. Chem. 2005, 70: 2191

<A NAME="RU05809ST-6C">6c</A> Mino T. Shirae Y. Sasai Y. Sakamoto M. Fujita T. J. Org. Chem. 2006, 71: 6834

<A NAME="RU05809ST-7A">7a</A> Hurtley WRH. J. Chem. Soc. 1929, 1870

<A NAME="RU05809ST-7B">7b</A> Bruggink A. Ray SJ. McKillop A. Org. Synth. 1978, 58: 52

We tried the reaction at 110 ˚C in toluene for 24 h, however, the yield of 2a decreased to 28% and ethyl phenylacetate was also obtained (8% NMR yield).

General procedure for copper-catalyzed C-arylation of diethyl malonate with aryl iodides (Table 2): Under an atmosphere of air, aryl iodide (2.0 mmol) was added to a mixture of diethyl malonate (4.0 mmol), Cs₂CO₃ (4.0 mmol), ligand 1a (0.20 mmol), and CuI (0.10 mmol) in toluene (2 mL) at r.t. The mixture was stirred at 90 ˚C for 24 h, then diluted with EtOAc and H₂O. The organic layer was washed with brine, dried over MgSO₄, and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (hexane-EtOAc) to provide the desired product. All prepared compounds 2, except 2f, were previously known and identified by ^¹H NMR, ^¹³C NMR and MS.
Compound 2f (Table [²] , entry 6): Yield: 53%; brown liquid; ^¹H NMR (CDCl₃): δ = 1.26 (t, J = 7.1 Hz, 6 H), 2.35 (s, 3 H), 4.16-4.27 (m, 4 H), 4.57 (s, 1 H), 7.13-7.28 (m, 4 H); ^¹³C NMR (CDCl₃): δ = 14.0, 21.4, 57.9, 61.7, 126.3, 128.4, 128.9, 129.9, 132.6, 138.2, 168.2; EI-MS: m/z (%) = 250 (25) [M⁺]; HRMS (FAB-MS): m/z calcd for C₁₄H₁₉O₄: 251.1283; found: 251.1284.

<A NAME="RU05809ST-10">10</A> Liu Y.-H. Li G. Yang L.-M. Tetrahedron Lett. 2009, 50: 343

General procedure for copper-catalyzed O-arylation of phenols with aryl bromides (Table 4): Under an atmosphere of air, aryl bromide (0.5 mmol) was added to a mixture of phenol (1.0 mmol), K₃PO₄ (1.0 mmol), ligand 1b (0.025 mmol), and CuI (0.025 mmol) in toluene (1 mL) at r.t. The mixture was stirred at 110 ˚C for either 5 h or 18 h, then the mixture was diluted with EtOAc and H₂O. The organic layer was washed with brine, dried over MgSO₄, and concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (hexane-EtOAc) to provide the desired product. All prepared compounds 3, except 3g and 3h, were known and identified by ^¹H NMR, ^¹³C NMR and MS.
Compound 3g (Table [4] , entry 7): Yield: 74%; colorless oil; ^¹H NMR (CDCl₃): δ = 2.34 (s, 3 H), 6.88 (d, J = 7.6 Hz, 2 H), 6.94-6.97 (m, 2 H), 7.15 (d, J = 8.6 Hz, 2 H), 7.35 (t, J = 8.0 Hz, 1 H), 7.45-7.54 (m, 2 H), 7.58 (d, J = 8.2 Hz, 1 H), 7.84-7.87 (m, 1 H), 8.22-8.25 (m, 1 H); ^¹³C NMR (CDCl₃): δ = 20.7, 112.6, 118.8, 122.1, 122.9, 125.8, 125.8, 126.5, 126.7, 127.7, 130.3, 132.8, 134.9, 153.6, 155.3; EI-MS: m/z (%) = 234 (100) [M⁺]; HRMS (FAB-MS): m/z calcd for C₁₇H₁₄O: 234.1045; found: 234.1027.
Compound 3h (Table [4] , entry 8): Yield: 78%; colorless oil; ^¹H NMR (CDCl₃): δ = 2.31 (s, 3 H), 2.33 (s, 3 H), 6.77-6.80 (m, 2 H), 6.87-6.93 (m, 3 H), 7.12-7.21 (m, 3 H); ^¹³C NMR (CDCl₃): δ = 20.7, 21.4, 115.3, 119.0, 119.1, 123.6, 129.3, 130.2, 132.7, 140.0, 154.8, 157.7; EI-MS: m/z (%) = 198 (100) [M⁺]; HRMS (FAB-MS): m/z calcd for C₁₄H₁₄O: 198.1045; found: 198.1046.

Copper(I)-Catalyzed C-C and C-O Coupling Reactions Using Hydrazone ­Ligands

Copper(I)-Catalyzed C-C and C-O Coupling Reactions Using Hydrazone Ligands