High-Pressure Au-Catalyzed Cycloisomerization of Internal 1,6- and 1,7-Enynes

Published as part of the Special Section 9^th EuCheMS Organic Division Young Investigator Workshop

Abstract

The influence of high pressure (in the kbar region) on the outcome of the Au(I)-catalyzed cycloisomerization of 1,6- and 1,7-enynes is presented. The positive effect of pressure is particularly marked for reactions involving sterically biased substrates (e.g. 1,6-enynes bearing atert-butyl substituent at the alkyne moiety) and the challenging cyclization of internal 1,7-enynes.

Key words

high pressure - gold - enynes - cycloisomerization - homogenous catalysis

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• 17 Mixture 2b/3b (1:7): Prepared in the reaction of 1d following the general procedure with 2 mol% of [3,5-(t-Bu)₂PhO]₃PAuNTf₂ as the catalyst. The mixture of title compounds was isolated in 66% yield as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 5.14–5.18 (m, 1 H), 3.71 (s, 6 H), 2.94–2.99 (m, 2 H), 2.83 (br s, 2 H), 2.75 (br s, 2 H), 1.65 (s, 3 H), 1.63 (s, 3 H), 1.57 (s, 3 H). Compound 3d: ¹³C NMR (101 MHz, CDCl₃): δ = 172.7, 140.4, 125.7, 124.7, 121.0, 59.2, 52.7, 42.8, 40.5, 35.8, 20.5, 20.3, 18.3. ¹H NMR (400 MHz, CDCl₃): δ = 6.09 (d, J = 16.1 Hz, 1 H), 5.60 (d, J = 16.0 Hz, 1 H), 5.42–5.46 (m, 1 H), 3.73 (s, 6 H), 3.10 (s, 2 H), 3.07 (s, 2 H), 1.02 (s, 9 H). Compound 2d: ¹H NMR (400 MHz, CDCl₃): δ = 6.09 (d,J = 16.1 Hz, 1 H), 5.60 (d, J = 16.1 Hz, 1 H), 5.42–5.46 (m, 1 H), 3.73 (s, 6 H), 3.10 (s, 2 H), 3.07 (s, 2 H), 1.02 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃): δ = 172.6, 143.3, 139.7, 124.0, 120.6, 58.6, 52.8, 40.8, 39.9, 33.1, 31.1, 29.5. IR (CH₂Cl₂): 2954, 2866 (C–H), 1739 (C=O), 1642 (C=C), 1436, 1362, 1256, 1218, 1201 (C–O), 1073, 971 cm^–1. HRMS (ESI): m/z [M + Na⁺] calcd for C₁₅H₂₂O₄Na: 289.1416; found: 289.1417.
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• 25 Compound 7d: Prepared in the reaction of 6d following the general procedure with 0.5 mol% of PPh₃AuNTf₂ as the catalyst. The title compound was isolated in 61% yield as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 5.09 (s, 1 H), 3.70 (s, 6 H), 2.65 (d, J = 17.1 Hz, 1 H), 2.34–2.42 (m, 1 H), 2.18–2.29 (m, 2 H), 1.68 (s, 3 H), 164 (s, 3 H), 1.62 (d, J = 1.2 Hz, 3 H), 1.51 (dd, J = 13.0, 10.8 Hz, 1 H), 1.02 (d, J = 6.8 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 172.7, 171.4, 137.1, 130.4, 127.7, 125.9, 54.1 52.5, 52.3, 36.1, 32.9, 27.9, 21.5, 21.2, 19.9, 17.5. IR (CH₂Cl₂): 2954, 2925 (C–H), 1738 (C=O), 1448, 1435, 1373, 1249, 1200 (C–O), 1084, 1038, 974 cm^–1. HRMS (ESI): m/z [M + Na⁺] calcd for C₁₆H₂₄O₄Na: 303.1572; found: 303.1570.
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• 28 Compound 16a: Prepared in the reaction of 15a following the general procedure (10 kbar) with 2 mol% of PPh₃AuNTf₂ as the catalyst. The title compound was isolated in 65% yield as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 5.23–5.27 (m, 1 H), 3.71 (s, 6 H), 2.55–2.62 (m, 2 H), 2.17 (t, J = 6.4 Hz, 2 H), 1.98–2.06 (m, 2 H), 1.62 (s, 6 H), 1.55 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 172.2, 140.4, 130.8, 125.4, 119.3, 52.8, 52.5, 30.7, 28.1, 24.7, 21.2, 19.8, 17.9. IR (CH₂Cl₂): 2952, 2917 (C–H), 1737 (C=O), 1435, 1326, 1253, 1216 (C–O), 1086, 1060 cm^–1. HRMS (ESI): m/z [M + Na⁺] calcd for C₁₅H₂₂O₄Na: 289.1416; found: 289.1413.