Designed Rearrangement of a Spirodiepoxide

 

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Abstract

Epoxidation of a highly functionalized aryl allene gave a rearranged enone.

References and Notes

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For a closely related stereoselective allene oxidation, see ref. 5b.

Selected Analytical Data:
Compound 25: ¹H NMR (400 MHz, CCl₃): δ = -0.08 (s, 9 H), 0.06 (d, J = 2.1 Hz, 6 H), 0.53 (q, J = 7.9 Hz, 6 H), 0.74 (t, J = 7.9 Hz, 9 H), 0.88 (s, 9 H), 1.81 (dd, J = 1.8, 5.8 Hz, 2 H), 3.56 (dd, J = 5.7, 9.9 Hz, 1 H), 3.64 (dd, J = 5.7, 10 Hz, 1 H), 3.90 (s, 3 H), 4.18 (m, 1 H), 5.25 (td, J = 2.4, 7.8 Hz, 1 H) 7.24 (s, 1 H), 7.54 (m, 3 H), 7.89 (d, J = 7.2 Hz, 2 H), 8.68 (s, 1 H), 8.72 (br, 1 H), 10.00 (s, 1 H). IR (neat): ν_max = 3403, 2721, 1953, 1700, 1581, 1259, 1001 cm^-1. ESI-MS: m/z calcd for C₃₆H₅₇NO₅Si₃Na [MNa]⁺: 691.0; found 690.5.
Compound 26: ¹H NMR (300 MHz, CCl₃): δ = 0.10 (s, 3.8 H), 0.11 (s, 2.8 H), 0.42-0.54 (m, 6 H), 0.76-0.89 (m, 18 H), 3.44-3.52 (m, 1 H), 3.60-3.69 (m, 0.73 H), 3.73-3.78 (m, 1.13 H), 3.84 (s, 3 H), 4.02-4.08 (m, 0.48 H), 4.15-4.20 (m, 0.65 H), 4.73 (d, J = 2.4 Hz, 0.66 H), 4.75 (d, J = 2.4 Hz, 0.36 H), 5.88 (s, 0.68 H), 5.97 (s, 0.27 H), 6.54 (s, 0.71 H), 6.68 (s, 0.28 H), 7.45-7.58 (m, 4 H), 7.86 (d, J = 7.5 Hz, 2 H), 8.53 (s, 1 H), 8.73 (br, 0.31 H), 8.86 (br, 0.65 H), 10.01 (s, 1 H). IR (neat): ν_max = 3387, 1728, 1691, 1578, 1261, 1013, 842 cm^-1. ESI-MS: m/z calcd for C₃₆H₅₇NO₇Si₃Na [MNa]⁺: 723.0; found: 722.3.