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Synlett 2007(9): 1395-1398  
DOI: 10.1055/s-2007-980352
LETTER
© Georg Thieme Verlag Stuttgart · New York

Rhodium-Complex-Catalyzed [2+2+2] Cycloaddition of Diynes and Carbonyl Compounds

Kyoji Tsuchikama, Yusuke Yoshinami, Takanori Shibata*
Department of Chemistry, School of Science and Engineering, Waseda University, Shinjuku, Tokyo, 169-8555, Japan
Fax: +81(3)52868098; e-Mail: tshibata@waseda.jp;
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Publication History

Received 13 March 2007
Publication Date:
23 May 2007 (online)

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Abstract

A Rh-BINAP complex was used to catalyze the hetero-[2+2+2] cycloaddition of symmetrical 1,6-diynes and carbonyl moiety of ketoesters, a diketone, and an aldehyde to give bicyclic α-pyrans, which were readily transformed into monocyclic compounds via the following electrocyclic ring opening. In the reaction of an unsymmetrical 1,6-diyne and a 1,7-diyne, α-pyrans with a quaternary carbon stereocenter were obtained in moderate to excellent ee using a chiral rhodium catalyst.

Key words

carbonyl - catalysis - cycloadditions - diynes - rhodium

    References and Notes

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13

Spectral data for 3aa: 1H NMR (600 MHz, CD2Cl2): δ = 1.53 (s, 3 H), 1.74 (s, 3 H), 1.78 (s, 3 H), 2.92 (d, J = 17.5 Hz, 1 H), 2.97 (d, J = 17.5 Hz, 1 H), 3.00 (d, J = 16.5 Hz, 1 H), 3.03 (d, J = 16.5 Hz, 1 H), 3.64 (s, 3 H), 5.09-5.14 (m, 4 H), 7.24-7.35 (m, 10 H). 13C NMR (150 MHz, CD2Cl2): δ = 14.0, 15.9, 21.7, 35.2, 36.4, 51.6, 59.3, 66.8, 66.8, 81.1, 110.1, 114.8, 127.5, 127.5, 127.9, 127.9, 128.1, 128.2, 131.1, 135.3, 135.4, 143.6, 170.4, 170.5, 173.1.

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Typical Experimental Procedure (Table 1, Entry 5): Under an atmosphere of argon, [Rh(cod)2]BF4 (2.2 mg, 5 µmol) and rac-BINAP (3.0 mg, 5 µmol) were placed in a flask and degassed CH2Cl2 (1.0 mL) was added. At r.t., the resultant solution was stirred, hydrogen gas was introduced into the flask, and then the solution was stirred for further 30 min. After the solvent and hydrogen were removed under reduced pressure, argon gas was introduced. To the flask was added a CH2Cl2 solution (1.0 mL) of diyne 1a (39.1 mg, 0.10 mmol) and methyl pyruvate (32.6 mg, 0.32 mmol); diyne 1a was consumed within 10 min. The resultant solution was stirred for further 44 h at r.t. until the bicyclic product 3aa completely disappeared. The solvent was evaporated under reduced pressure, and the obtained crude products were purified by TLC (hexane-EtOAc, 3:1) to give analytically pure 4aa (47.6 mg, 96%, Z/E = 7:1). (Z)-4aa: IR (CH2Cl2): 1734, 1658, 1240, 750, 698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 1.91 (s, 3 H), 1.93 (s, 3 H), 2.11 (s, 3 H), 3.34 (s, 2 H), 3.35 (s, 2 H), 3.55 (s, 3 H), 5.09-5.17 (m, 4 H), 7.23-7.31 (m, 10 H). 13C NMR (100 MHz, CDCl3): δ = 15.1, 19.5, 28.5, 40.9, 45.5, 51.7, 57.0, 67.5, 125.5, 128.0, 128.3, 128.5, 132.1, 135.3, 142.0, 154.2, 167.8, 170.8, 195.7. HRMS: m/z [M + H] calcd for C29H31O7: 491.2070; found: 491.2030.

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Spectral data for 3da: [α]26 D 123.1 (c = 0.64, toluene). IR (neat): 1736, 1244, 696 cm-1. 1H NMR (500 MHz, C6D6): δ = 1.74 (s, 3 H), 1.83 (s, 3 H), 3.23 (s, 2 H), 3.37, (s, 3 H), 3.58 (d, J = 16.0 Hz, 1 H), 3.71 (d, J = 16.0 Hz, 1 H), 4.95-5.10 (m, 4 H), 7.10-7.27 (m, 13 H), 7.95 (d, J = 8.0 Hz, 2 H). 13C NMR (125 MHz, C6D6): δ = 15.3, 23.0, 37.6, 38.1, 52.1, 60.9, 67.5, 67.6, 81.8, 113.1, 119.1, 127.9, 128.3, 128.4, 128.4, 128.6, 128.7, 128.7, 129.0, 129.0, 133.4, 135.5, 136.4, 136.4, 144.8, 170.9, 171.1, 173.7. HRMS: m/z [M + H] calcd for C34H33O7: 553.2226; found: 553.2240. The ee was determined by HPLC analysis using a chiral column [Daicel Chiralpak AD-H: 4 × 250 mm, UV detector: λ = 254 nm, r.t., eluent: 3% i-PrOH in hexane, flow rate: 1.0 mL/min, t R (minor isomer) = 21 min, t R (major isomer) = 24 min].

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Rh-(R)-BINAP catalyst gave the opposite enantiomer with 96% ee.

18

Cycloadduct 3da also underwent the ring-opening reaction very slowly but its rate was almost the same with or without Rh-(S)-BINAP catalyst. In fact, when the ring-opening reaction of racemic 3da was examined in the presence of Rh-(S)-BINAP catalyst, the remaining 3da was racemic and kinetic resolution did not proceed.