The Gold(I)-Catalyzed Cycloisomerization of 1,6-Enynes to 1,4-Dienes

Sang Ick Lee; Soo Min Kim; Sun Young Kim; Young Keun Chung

doi:10.1055/s-2006-949629

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Synlett 2006(14): 2256-2260
DOI: 10.1055/s-2006-949629

LETTER

The Gold(I)-Catalyzed Cycloisomerization of 1,6-Enynes to 1,4-Dienes

Sang Ick Lee, Soo Min Kim, Sun Young Kim, Young Keun Chung*
Intelligent Textile System Research Center, and Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-747, Korea
Fax: +82(2)8890310; e-Mail: ykchung@snu.ac.kr;

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Publication History

Received 17 May 2006
Publication Date:
24 August 2006 (online)

Abstract
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Abstract

Cycloisomerization of 1,6-enynes to 1,4-dienes proceeded smoothly in the presence of a gold(I) catalyst under mild reaction conditions, and cyclized 1,4-dienes were isolated in good yields. The catalytic system can tolerate the oxygen and nitrogen tether in the substrate.

Key words

gold - enyne - isomerization - 1,4-diene - catalysis

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5

Lee, S. I.; Kim, S. M.; Kim, S. Y.; Choi, M. R.; Chung, Y. K., manuscript in preparation.

13

General Procedure for Au(I)-Catalzyed Cycloisomerization of 1,6-Enynes to 1,4-Dienes: To a flame-dried 15-mL Schlenk flask capped with a rubber septum, CH₂Cl₂ (5 mL) was injected via syringe under N₂ flow. (PPh₃)AuCl (13 mg, 5 mol%) and AgOTf (16 mg, 7 mol%) were added sequentially. The Au solution was stirred for 10 min. An enyne (0.73 mmol) was put into the flask under N₂ flow. The reaction was monitored by TLC. After the reactant was disappeared, the solvent was removed under reduced pressure. A flash chromatography on a silica gel eluting with hexane and EtOAc (10:1) gave the product.
4-Methyl- N -(3-methylbut-2-enyl)- N -(3-phenylprop-2-ynyl)benzenesulfonamide ( 1a): ¹H NMR (300 MHz, CDCl₃): δ = 1.72 (s, 3 H), 1.77 (s, 3 H), 2.34 (s, 3 H), 3.90 (d, J = 7.2 Hz, 2 H), 4.30 (s, 2 H), 5.20 (m, 1 H), 7.05 (m, 2 H), 7.29 (m, 5 H), 7.80 (d, J = 8.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 17.9, 21.4, 25.9, 36.3, 44.2, 82.3, 85.4, 118.1, 122.4, 127.9, 128.1, 128.3, 129.4, 131.4, 136.1, 139.0, 143.3. MS (EI): m/z calcd for C₂₁H₂₃N₁S₁O₂: 353.1450; found: 353.1451.
( E )-3-Benzylidene-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2a) (Figure 1): ¹H NMR (300 MHz, CDCl₃): δ = 1.74 (s, 3 H), 2.42 (s, 3 H), 2.94 (dd, J = 4.3, 11.5 Hz, 1 H), 3.38 (s, 1 H), 3.48 (td, J = 2.7, 17.0 Hz, 1 H), 3.64 (dd, J = 3.4, 11.6 Hz, 1 H), 3.99 (dd, J = 3.1, 17.0 Hz, 1 H), 4.78 (s, 3 H), 4.88 (s, 3 H), 6.03 (t, J = 3.4 Hz, 1 H), 7.22 (m, 1 H), 7.27 (m, 4 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.70 (d, J = 8.3 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.4, 21.6, 44.9, 45.4, 47.4, 115.2, 120.9, 125.8, 127.5, 127.8, 128.4, 129.8, 133.2, 137.6, 139.8, 143.6, 143.7. MS (EI): m/z calcd for C₂₁H₂₃N₁S₁O₂: 353.1450; found: 353.1454. The ee value was determined to be 22% by HPLC analysis using a chiral column Chiralcel OD-H (254 nm UV detector, r.t., eluent: 3% i-PrOH in hexane, flow rate: 0.5 mL/min, t _R(major) = 34 min and t _R(minor) = 40 min]; [α]_D ¹⁸ +50.32 (c = 1.00 in CHCl₃).
7,7-Dimethyl-6-phenyl-3-tosyl-3-azabicyclo[4.1.0]hept-4-ene ( 3a): ¹H NMR (300 MHz, CDCl₃): δ = 0.81 (s, 3 H), 1.04 (s, 3 H), 1.55 (d, J = 5.6 Hz, 1 H), 2.51 (s, 3 H), 3.62 (dd, J = 5.9, 12.2 Hz, 1 H), 3.79 (d, J = 12.2 Hz, 1 H), 5.16 (d, J = 8.3 Hz, 1 H), 6.67 (d, J = 8.4 Hz, 1 H), 7.16 (d, J = 7.1 Hz, 2 H), 7.25 (m, 1 H), 7.31 (d, J = 7.6 Hz, 2 H), 7.39 (d, J = 7.9 Hz, 2 H), 7.77 (d, J = 8.1 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 16.1, 21.8, 25.0, 27.4, 30.5, 31.1, 39.0, 110.6, 121.7, 126.4, 127.4, 128.6, 128.9, 129.9, 135.1, 142.6, 143.9. MS (EI): m/z calcd for C₂₁H₂₃N₁S₁O₂: 353.1450; found: 353.1446.
2,4,6-Trimethyl- N -(3-methylbut-2-enyl)- N -(3-phenyl-prop-2-ynyl)benzenesulfonamide ( 1b): ¹H NMR (300 MHz, CDCl₃): δ = 1.69 (s, 3 H), 1.73 (s, 3 H), 2.28 (s, 3 H), 2.65 (s, 6 H), 3.89 (d, J = 7.4 Hz, 2 H), 4.19 (s, 2 H), 5.13 (t, J = 7.4 Hz, 1 H), 6.95 (s, 2 H), 7.31 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.0, 21.2, 23.1, 26.2, 35.2, 43.6, 77.2, 83.8, 118.5, 122.8, 128.4, 131.9, 132.2, 133.0, 138.9, 140.6. MS (EI): m/z calcd for C₂₃H₂₇N₁S₁O₂: 381.1763; found: 381.1766.
( E )-3-Benzylidene-1-(mesitylsulfonyl)-4-(prop-1-en-2-yl)pyrrolidine ( 2b): ¹H NMR (300 MHz, CDCl₃): δ = 1.46 (s, 3 H), 2.29 (s, 3 H), 2.63 (s, 6 H), 3.22 (dd, J = 4.2, 11.8 Hz, 1 H), 3.29 (m, 1 H), 3.51 (dd, J = 3.1, 11.8 Hz, 1 H), 3.85 (m, 1 H), 4.00 (m, 1 H), 4.69 (s, 1 H), 4.76 (s, 1 H), 6.14 (t, J = 3.4 Hz, 1 H), 6.94 (s, 2 H), 7.25 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.08, 21.1, 23.3, 43.9, 45.7, 115.5, 121.5, 125.7, 127.5, 128.5, 131.7, 131.9, 132.1, 137.6, 139.9, 141.0, 142.9, 143.1. MS (EI): m/z calcd for C₂₃H₂₇N₁S₁O₂: 381.1763; found: 381.1766.
( E )-3-Benzylidene-4-(prop-1-en-2-yl)tetrahydrofuran ( 2c): ¹H NMR (300 MHz, CDCl₃): δ = 1.76 (s, 3 H), 3.22 (s, 1 H), 3.83 (dd, J = 4.0, 11.1 Hz, 1 H), 3.94 (dd, J = 2.7, 11.1 Hz, 1 H,), 4.33 (m, 2 H), 4.81 (s, 1 H), 4.88 (s, 1 H) 6.19 (t, J = 2.7 Hz, 1 H), 7.29 (m, 5 H) ¹³C NMR (75 MHz, CDCl₃): δ = 21.7, 44.6, 66.3, 68.9, 114.2, 124.3, 125.6, 127.4, 128.5, 136.5, 140.1, 145.0. MS (EI): m/z calcd for C₁₄H₁₆O₁: 200.1201; found: 200.1202.
N -(But-2-ynyl)-4-methyl- N -(3-methylbut-2-enyl)ben-zenesulfonamide ( 1d): ¹H NMR (300 MHz, CDCl₃): δ = 1.53 (s, 3 H), 1.66 (s, 3 H), 1.71 (s, 3 H), 2.42 (s, 3 H), 3.78 (d, J = 7.2 Hz, 2 H), 3.99 (d, J = 2.1 Hz, 2 H), 5.10 (t, J = 7.2 Hz, 1 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.74 (d, J = 8.2 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 3.4, 17.9, 21.7, 26.0, 36.2, 44.1, 72.4, 81.4, 118.5, 128.1, 129.4, 136.6, 138.7, 143.2. HRMS (FAB): m/z calcd for C₁₆H₂₁N₁S₁O₂: 292.1371; found: 292.1375.
( E )-3-Ethylidene-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2d): ¹H NMR (300 MHz, CDCl₃): δ = 1.60 (s, 3 H), 1.72 (s, 3 H), 2.43 (s, 3 H), 2.74 (m, 1 H), 2.93 (dd, J = 4.9, 11.5 Hz, 1 H), 3.30 (m, 1 H), 3.34 (m, 1 H), 3.67 (m, 1 H), 4.78 (s, 1 H), 4.90 (m, 1 H), 5.45 (t, J = 5.6 Hz, 1 H), 7.31 (d, J = 8.1 Hz, 2 H), 7.65 (d, J = 8.3 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 20.5, 21.4, 21.6, 44.9, 47.2, 47.7, 114.3, 118.6, 127.9, 128.0, 129.7, 134.1, 143.6, 144.1. MS (EI): m/z calcd for C₁₆H₂₁N₁S₁O₂: 292.1371; found: 292.1375.
N -(3-Cyclopropylprop-2-ynyl)-4-methyl- N -(3-methyl-but-2-enyl)benzenesulfonamide ( 1e): ¹H NMR (300 MHz, CDCl₃): δ = 0.29 (m, 2 H), 0.58 (m, 2 H), 0.93 (m, 1 H), 1.62 (s, 3 H) 1.69 (s, 3 H), 2.40 (s, 3 H), 3.75 (d, J = 7.3 Hz, 2 H), 3.97 (d, J = 1.9 Hz, 2 H), 5.08 (t, J = 7.3 Hz, 1 H), 7.25 (d, J = 8.3 Hz, 2 H), 7.69 (d, J = 8.3 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = -0.9, 7.8, 17.9, 21.5, 25.9, 36.1, 43.9, 68.2, 89.1, 118.3, 127.9, 129.3, 136.4, 138.6, 143.2. MS (EI): m/z calcd for C₁₈H₂₃N₁S₁O₂: 317.1450; found: 317.1447.
( E )-3-(Cyclopropylmethylene)-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2e): ¹H NMR (300 MHz, CDCl₃): δ = 0.45 (m, 1 H), 0.56 (m, 1 H), 1.20 (m, 2 H), 1.77 (s, 3 H), 2.41 (s, 3 H), 2.87 (m, 2 H), 3.30 (d, J = 15.9 Hz, 1 H), 3.39 (d, J = 7.6 Hz, 1 H), 3.72 (m, 1 H), 4.83 (s, 1 H), 4.91 (s, 1 H), 5.31 (t, J = 3.3 Hz, 1 H), 7.30 (d, J = 8.5 Hz, 1 H), 7.64 (d, J = 8 3 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 5.6, 6.2, 14.9, 20.8, 21.4, 44.8, 46.6, 47.3, 114.3, 115.1, 127.7, 129.5, 133.4, 139.3, 143.4, 144.4. MS (EI): m/z calcd for C₁₈H₂₃N₁S₁O₂: 317.1450; found: 317.1444.
6-Cyclopropyl-7,7-dimethyl-3-tosyl-3-azabicyclo[4.1.0]hept-4-ene ( 3e): ¹H NMR (300 MHz, CDCl₃): δ = 0.05 (m, 2 H), 0.42 (m, 2 H), 0.69 (d, J = 6.2 Hz, 1 H), 0.76 (s, 3 H), 0.91 (m, 1 H), 1.14 (s, 3 H), 2.42 (s, 3 H), 3.28 (dd, J = 6.3, 12.2 Hz, 1 H), 3.45 (dd, J = 1.5, 12.2 Hz, 1 H), 4.90 (dd, J = 0.9, 8.5 Hz, 1 H), 6.54 (d, J = 8.5 Hz, 1 H), 7.29 (d, J = 8.1 Hz, 2 H), 7.64 (d, J = 8.3 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 3.5, 4.9, 12.9, 16.5, 21.5, 22.5, 25.4, 29.0, 38.8, 108.8, 121.5, 127.1, 129.6, 135.0, 143.6. MS (EI): m/z calcd for C₁₈H₂₃N₁S₁O₂: 317.1450; found: 317.1447.
N-(3-Cyclohexenylprop-2-ynyl)-4-methyl- N -(3-methylbut-2-enyl)benzenesulfonamide ( 1f): ¹H NMR (300 MHz, CDCl₃): δ = 1.53 (m, 4 H), 1.67 (s, 3 H), 1.72 (s, 3 H), 1.79 (dd, J = 5.4, 7.3 Hz, 2 H), 2.01 (d, J = 1.7 Hz, 2 H), 2.41 (s, 3 H), 3.80 (d, J = 7.3 Hz, 2 H), 4.16 (s, 2 H), 5.13 (t, J = 7.3 Hz, 1 H), 5.76 (ddd, J = 1.7, 3.8, 5.6 Hz, 1 H), 7.27 (d, J = 8.7 Hz, 2 H), 7.74 (d, J = 8.3 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.1, 21.62, 21.69, 22.4, 25.7, 26.1, 29.1, 36.6, 44.2, 79.6, 87.4, 118.4, 120.1, 128.1, 129.5, 135.1, 136.6, 138.9, 143.2. MS (EI): m/z calcd for C₂₁H₂₇N₁S₁O₂: 357.1763; found: 357.1757.
( E )-3-(Cyclohexenylmethylene)-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2f): ¹H NMR (300 MHz, CDCl₃): δ = 1.53 (m, 2 H), 1.61 (m, 2 H), 1.78 (s, 3 H), 2.06 (m, 4 H), 2.42 (s, 3 H), 2.79 (dd, J = 4.0, 11.4 Hz, 1 H), 3.12 (s, 1 H), 3.35 (d, J = 17.0 Hz, 1 H), 3.64 (dd, J = 2.6, 11.5 Hz, 1 H), 3.93 (d, J = 3.9 Hz, 1 H), 4.71 (s, 1 H), 4.88 (s, 1 H), 5.67 (t, J = 3.5 Hz, 1 H), 5.71 (s, 1 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.66 (d, J = 8.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.56, 21.62, 22.3, 22.9, 25.8, 25.9, 43.3, 45.3, 47.7, 113.9, 116.9, 124.5, 127.9, 129.7, 133.7, 134.5, 138.3, 143.5, 144.8. MS (EI): m/z calcd for C₂₁H₂₇N₁S₁O₂: 357.1763; found: 357.1765.
N -[3-(4-Methoxyphenyl)prop-2-ynyl]-4-methyl- N -(3-methylbut-2-enyl)benzenesulfonamide ( 1g): ¹H NMR (300 MHz, CDCl₃): δ = 1.69 (s, 3 H), 1.73 (s, 3 H), 2.33 (s, 3 H), 3.77 (s, 3 H), 3.88 (d, J = 7.3 Hz, 2 H), 4.23 (s, 2 H), 5.16 (t, J = 7.3 Hz, 1 H), 6.75 (d, J = 6.8 Hz, 2 H), 6.99 (d, J = 6.8 Hz, 2 H), 7.23 (d, J = 8.0 Hz, 2 H), 7.76 (d, J = 8.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.0, 21.5, 26.0, 36.5, 44.2, 55.4, 80.8, 85.4, 113.8, 114.5, 118.3, 127.9, 129.5, 133.0, 136.3, 138.9, 143.3, 159.7. MS (HRFAB): m/z calcd for C₂₂H₂₅N₁S₁O₃: 383.1555; found: 383.1555.
( E )-3-(4-Methoxybenzylidene)-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2g): ¹H NMR (300 MHz, CDCl₃): δ = 1.74 (s, 3 H), 2.42 (s, 3 H), 2.94 (dd, J = 4.3, 11.6 Hz, 1 H), 3.34 (s, 3 H), 3.48 (m, 1 H), 3.64 (dd, J = 3.2, 11.5 Hz, 1 H), 3.77 (s, 1 H), 3.98 (dd, J = 3.5, 16.8 Hz, 1 H), 4.78 (s, 1 H), 4.88 (s, 1 H), 5.95 (t, J = 3.4 Hz, 1 H), 6.80 (d, J = 9.0 Hz, 2 H), 7.21 (d, J = 8.8 Hz, 2 H), 7.32 (m, 2 H), 7.69 (m, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.4, 21.7, 45.2, 45.4, 47.6, 55.4, 113.9, 115.2, 119.5, 126.9, 127.9, 129.8, 132.5, 133.7, 137.2, 143.7, 143.9, 159.2. MS (HRFAB): m/z calcd for C₂₂H₂₅N₁S₁O₃: 383.1555; found: 383.1555.
4-Methyl- N -(3-methylbut-2-enyl)- N -[3-(naphthalen-1-yl)prop-2-ynyl]benzenesulfonamide ( 1h): ¹H NMR (300 MHz, CDCl₃): δ = 1.70 (s, 3 H), 1.77 (s, 3 H), 2.12 (s, 3 H), 3.97 (d, J = 7.2 Hz, 2 H), 4.46 (s, 2 H), 5.24 (t, J = 7.2 Hz, 1 H), 7.14 (d, J = 8.1 Hz, 2 H), 7.33 (m, 2 H), 7.48 (m, 2 H), 7.82 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 18.0, 21.3, 26.0, 36.6, 44.3, 83.6, 87.1, 118.1, 120.1, 125.0, 125.9, 126.4, 126.6, 127.8, 128.2, 128.8, 129.5, 130.5, 132.9, 133.0, 135.9, 139.2, 143.4. MS (EI): m/z calcd for C₂₅H₂₅N₁S₁O₂: 403.1606; found: 403.1601.

( E )-3-(Naphthalen-1-ylmethylene)-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2h): ¹H NMR (300 MHz, CDCl₃): δ = 1.67 (s, 3 H), 2.45 (s, 3 H), 3.23 (dd, J = 4.4, 11.5 Hz, 1 H), 3.46 (s, 1 H), 3.61 (m, 2 H), 4.03 (d, J = 15.1 Hz, 1 H), 4.70 (s, 1 H), 4.72 (s, 1 H), 5.84 (t, J = 2.9 Hz, 1 H), 7.17 (d, J = 6.3 Hz, 1 H), 7.40 (m, 5 H), 7.79 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.4, 21.7, 45.2, 47.5, 47.6, 114.9, 124.4, 125.2, 125.3, 125.7, 125.8, 125.9, 127.7, 127.9, 128.7, 129.9, 131.3, 133.2, 133.9, 137.7, 138.9, 143.6, 143.8. MS (EI): m/z calcd for C₂₅H₂₅N₁S₁O₂: 403.1606; found: 403.1604.
N -[3-(3,5-Dimethylphenyl)prop-2-ynyl]-4-methyl- N -(3-methylbut-2-enyl)benzenesulfonamide ( 1i): ¹H NMR (300 MHz, CDCl₃): δ = 1.68 (s, 3 H), 1.72 (s, 3 H), 2.20 (s, 6 H), 2.28 (s, 3 H), 3.88 (d, J = 7.3 Hz, 2 H), 4.27 (s, 2 H), 5.17 (t, J = 7.3 Hz, 1 H), 7.05 (m, 2 H), 7.23 (m, 3 H), 7.77 (d, J = 8.2 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 14.8, 21.8, 27.4, 27.5, 31.1, 40.7, 117.8, 119.8, 126.7, 127.3, 128.6, 129.4, 130.0, 134.8, 140.7, 144.0. MS (EI): m/z calcd for C₂₃H₂₇N₁S₁O₂: 381.1763; found: 381.1762.
( E )-3-(3,5-Dimethylbenzylidene)-4-(prop-1-en-2-yl)-1-tosylpyrrolidine ( 2i): ¹H NMR (300 MHz, CDCl₃): δ = 1.75 (s, 3 H), 2.26 (s, 6 H), 2.40 (s, 3 H), 2.92 (dd, J = 4.3, 11.6 Hz, 1 H), 3.36 (s, 1 H), 3.46 (dd, J = 2.6, 17.0 Hz, 1 H), 3.64 (dd, J = 3.3, 11.6 Hz, 1 H), 3.96 (dd, J = 3.6, 17.0 Hz, 1 H), 4.76 (s, 1 H), 4.86 (s, 1 H), 5.97 (t, J = 3.4 Hz, 1 H), 6.85 (s, 1 H), 6.87 (s, 2 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.68 (d, J = 8.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 21.42, 21.46, 21.6, 45.0, 45.4, 47.5, 115.0, 127.7, 123.7, 127.8, 129.2, 129.7, 133.7, 137.7, 138.0, 140.0, 143.6, 143.8. MS (EI): m/z calcd for C₂₃H₂₇N₁S₁O₂: 381.1763; found: 381.1761.
N -(But-2-enyl)-4-methyl- N -(3-phenylprop-2-ynyl)benzenesulfonamide ( 1k): ¹H NMR (300 MHz, CDCl₃): δ = 1.72 (d, J = 6.0 Hz, 3 H), 2.33 (s, 3 H), 3.82 (trans) (d, J = 6.6 Hz, 2 H), 3.95 (cis) (d, J = 7.2 Hz, 2 H), 4.30 (s, 2 H), 5.44 (m, 1 H), 5.75 (dt, J = 6.2, 12.8 Hz, 1 H), 7.07 (d, J = 6.6 Hz, 2 H), 7.25 (m, 5 H), 7.77 (d, J = 8.0 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 17.9, 21.6, 36.7, 48.8, 82.1, 85.8, 122.6, 124.9, 128.0, 128.3, 128.5, 129.7, 131.7, 131.8, 136.4, 143.5. MS (EI): m/z calcd for C₂₀H₂₁N₁S₁O₂: 339.1293; found: 339.1296.
7-Methyl-6-phenyl-3-tosyl-3-azabicyclo[4.1.0]hept-4-ene ( 3k): ¹H NMR (300 MHz, CDCl₃; cis compound): δ = 0.94 (d, J = 6.1 Hz, 3 H), 1.07 (m, 1 H), 1.55 (m, 1 H), 2.43 (s, 3 H), 3.50 (dd, J = 5.4, 11.0 Hz, 1 H), 3.65 (d, J = 11.0 Hz, 1 H), 5.15 (d, J = 8.4 Hz, 1 H), 6.74 (d, J = 8.4 Hz, 1 H), 7.15 (d, J = 6.9 Hz, 2 H), 7.26 (m, 5 H), 7.68 (d, J = 8.2 Hz, 2 H). ¹H NMR (300 MHz, CDCl₃; trans compound): δ = 0.67 (d, J = 6.3 Hz, 3 H), 1.07 (m, 1 H), 1.68 (m, 1 H), 2.43 (s, 3 H), 3.11 (dd, J = 2.5, 11.5 Hz, 1 H), 4.09 (d, J = 11.5 Hz, 1 H), 5.42 (d, J = 8.1 Hz, 1 H), 6.33 (d, J = 8.1 Hz, 1 H), 7.15 (d, J = 6.9 Hz, 2 H), 7.26 (m, 5 H), 7.70 (d, J = 8.2 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 14.8, 21.8, 27.4, 31.1, 40.7, 117.8, 119.8, 126.7, 127.3, 128.6, 129.4, 130.0, 134.8, 140.7, 144.0. MS (EI): m/z calcd for C₂₀H₂₁N₁S₁O₂: 339.1293; found: 339.1296.

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The Gold(I)-Catalyzed Cycloisomerization of 1,6-Enynes to 1,4-Dienes

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