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Synlett 2008(9): 1321-1324  
DOI: 10.1055/s-2008-1072614
LETTER
© Georg Thieme Verlag Stuttgart · New York

Gold(I)-Catalyzed Cycloisomerization of (Arene)chromium Complexes with Enyne Bonds Directed Towards Axially Chiral Biaryls

Christophe Michon, Suyun Liu, Shinya Hiragushi, Jun’ichi Uenishi, Motokazu Uemura*
Kyoto Pharmaceutical University, Yamashina, Kyoto 607-8412, Japan
Fax: +81(75)5954763; e-Mail: muemura@mb.kyoto-phu.ac.jp;
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Publication History

Received 14 February 2008
Publication Date:
07 May 2008 (online)

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Abstract

Planar chiral arene-chromium complexes with enyne bonds gave stereoselectively axially chiral biaryl-chromium complexes by gold(I)-catalyzed cycloisomerization in good yields.

Key words

arene complexes - catalysis - chirality - chromium - cycloisomerization - gold

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9

The stereochemistry at spiro quaternary carbon was assigned by reaction path; the double bond attack from exo side to the tricarbonylchromium fragment.

10

Typical Experimental Procedure
A mixture of chromium complex 1g (50 mg, 0.12 mmol), (PPh3)AuNTf2 (4.5 mg) in CH2Cl2 (5 mL) was heated at 40 °C for 5 h under argon. After filtration through Celite and evaporation under vacuum, the residue was purified by SiO2 chromatography (Et2O-hexane, 1:5) to give 48 mg (98%) of 2g; mp 209 °C (dec). 1H NMR (300 MHz, CDCl3): δ = 1.92 (3 H, s), 2.18 (3 H, s), 2.66 (3 H, s), 4.83 (1 H, d, J = 6.3Hz), 5.00 (1 H, d, J = 6.3Hz), 5.72 (1 H, t, J = 6.3Hz), 7.44-7.57 (2 H, m), 7.88 (1 H, s), 7.94 (1 H, d, J = 7.8 Hz), 8.04 (1 H, d, J = 7.8Hz). 13C NMR (75 MHz, CDCl3): δ = 15.27, 17.05, 19.64, 56.01, 70.67, 85.08, 95.06, 107.42, 113.45, 123.82, 125.18, 126.46, 129.22, 130.87, 131.84, 132.04, 132.07, 132.10, 132.80, 143.40, 233.78. IR (CHCl3): 1961, 1880
cm-1. Anal. Calcd for C23H20O4Cr: C, 66.98; H, 4.89. Found: C, 66.89; H, 4.97. The obtained chromium complex was exposed to sunlight in Et2O at 0 °C to give chromium-free biaryl compound in a quantitative yield.