Synthesis and Derivatization of Bis-nor Wieland-Miescher Ketone

Abstract

An efficient synthesis of bis-nor Wieland-Miescher ketone and its derivatives starting from commercially available 2-allyl-2-methylcyclopenta-1,3-dione is described.

Key words

alkylation - carbocycles - cyclization - epoxidation - Wittig reaction

References

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10

6-Allyl-6-methyldihydro-2H-pyran-2,5 (6H)-dione: ¹H NMR (CDCl₃): δ = 5.72 (m, 1 H, =CH), 5.13 and 5.15 (m, 2 H, =CH₂), 2.84 and 2.88 (m, 2 H, H-3), 2.73 and 2.60 (m, 2 H, H-4), 2.65 and 2.45 (tdd each, 2 H, J = 0.9, 0.9, 7.4, 14.1 Hz, CH ₂CH=CH₂), 1.48 (s, 3 H, CH₃). ¹³C NMR (CDCl₃): δ = 207.23 (C-5), 169.24 (C-2), 130.35 (=CH), 121.06 (=CH₂), 88.71 (C-6), 43.20 (CH₂CH=CH₂), 33.96 (C-4), 28.04 (C-3), 24.92 (CH₃).

13

Alternatively, a crystalline phosphonium salt can be isolated by filtration remaining by-product into solution. However, this isolation decreases the overall yield of compound 2 from 79% to 64%.