Designed Rearrangement of a Spirodiepoxide

Abstract

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

Key words

spirodiepoxide - allene - oxidation - acid-induced rearrangement - MCPBA

References and Notes

• 1a Crandall JK. Machleder WH. J. Am. Chem. Soc.  1968,  90:  7292 
• 1b Crandall JK. Machleder WH. Thomas MJ. J. Am. Chem. Soc.  1968,  90:  7346 
• 1c Crandall JK. Machleder WH. J. Am. Chem. Soc.  1968,  90:  7347 
• 1d Crandall JK. Machleder WH. Sojka SA. J. Org. Chem.  1973,  38:  1149 
• 1e Crandall JK. Conover WW. Komin JB. Machleder WH. J. Org. Chem.  1974,  39:  1723 
• 1f

  See also ref. 2.

• 2a Crandall JK. Batal DJ. Sebesta DP. Lin F. J. Org. Chem.  1991,  56:  1153 ; and references cited therein
• 2b

  See also ref. 4 and 5.

• 3 DMDO oxidations were conducted using acetone as solvent. Solutions of the oxidant were prepared by the method herein: Murray RW. Jeyaraman R. J. Org. Chem.  1985,  50:  2847 
• 4a Ghosh P. Lotesta SD. Williams LJ. J. Am. Chem. Soc.  2007,  129:  2438 
• 4b Lotesta SD. Kiren S. Williams LJ. Angew. Chem. Int. Ed.  2007,  46:  7108 
• 5a Katukojvala S. Barlett KN. Lotesta SD. Williams LJ. J. Am. Chem. Soc.  2004,  126:  15348 
• 5b Lotesta SD. Hou Y. Williams LJ. Org. Lett.  2007,  9:  869 ; and references cited therein
• 5c Shangguan N. Kiren S. Williams LJ. Org. Lett.  2007,  9:  1093 
• 6 McClure KF. Danishefsky SJ. J. Am. Chem. Soc.  1993,  115:  6094 
• 7 Dieck HA. Heck FR. J. Organomet. Chem.  1975,  93:  259 
• 8a Tang Y. Marshall JA. J. Org. Chem.  1993,  58:  3233 
• 8b Tang Y. Marshall JA. J. Org. Chem.  1994,  59:  1457 
• 9a Murray RW. Chem. Rev.  1989,  89:  1187 
• 9b Marples BA. Muxworthy JP. Baggaley KH. Synlett  1992,  646 
• 9c Csuk R. Dörr P. Tetrahedron  1994,  50:  9983 
• 11 For example, see: Fleming I. Hill JHM. Parker D. Waterson D. J. Chem. Soc., Chem. Commun.  1985,  318 

10

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

12

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.