Synlett 2018; 29(10): 1319-1323
DOI: 10.1055/s-0036-1591756
letter
© Georg Thieme Verlag Stuttgart · New York

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

Małgorzata Kocój
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland   Email: [email protected]
,
Elżbieta Jarosińska
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland   Email: [email protected]
,
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland   Email: [email protected]
› Author Affiliations
Financial support from the Polish National Science Centre (Grant decision DEC-2013/11/D/ST5/02979) and the Polish Ministry of Science and Higher Education (stipend for W.C.) is gratefully acknowledged.
Further Information

Publication History

Received: 28 October 2017

Accepted after revision: 02 January 2018

Publication Date:
02 February 2018 (online)


Published as part of the Special Section 9th 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.

Supporting Information

 
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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.