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Fringuelli, F.; Piermatti, O., Science of Synthesis: Water in Organic Synthesis, (2012) 1, 496.
[2,3]-Sigmatropic rearrangement of allyl sulfoxides (Mislow–Evans rearrangement[62,63]) bearing a hydroxy group at the γ-position occurs with high stereoselectivity to give (E)-δ-hydroxy enols.[64] Exposure of γ-hydroxy-substituted 3-alkoxyallyl sulfides 79 to sodium periodate in dioxane/water (5:1) at room temperature gives sulfoxides 80 (Scheme 21) that, via [2,3] rearrangement to 81, give exclusively (E)-δ-hydroxy enals 82 in excellent yields.[64] Both the hydroxy and alkoxy groups control the stereochemistry of the sigmatropic rearrangement. The reaction allows the synthesis of α,β-unsaturated δ-hydroxy enals which are otherwise difficult to obtain.
Meeeee 88 [8,8]-Meeeeeeeeee Meeeeeeeeeeee ee γ-Meeeeee-Meeeeeeeeee 8-Meeeeeeeeee Meeeeeeeee[88]
M8 | M8 | M8 | M8 | M8 | Meeee (%) | Meeee (M/M) | Mee |
---|---|---|---|---|---|---|---|
(MM8)8Me | M | M | M | Me | 88 | 88:8 | [88] |
Me | M | M | M | Me | 88 | 88:8 | [88] |
(MM8)8Me | M | M | Me | Me | 88 | 88:8 | [88] |
MM=MM8 | Me | M | Me | Me | 88 | 88:8 | [88] |
(MM8)8Me | M | Me | M | Me | 88 | 88:88 | [88] |
Meeeeeeeeeee Meeeeeeee
(M)-8-Meeeeeeeee-8-eeee [88, M8 = (MM8)8Me; M8 = M8 = M8 = M]; Meeeeee Meeeeeeee:[88]
M eeeee eeee ee eeeeeee/M8M (8:8; 8 eM) eeeeeeeeee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-ee-8-ee [88, M8 = (MM8)8Me; M8 = M8 = M8 = M; M8 = Me; 888 ee, 8.88 eeee] eee MeMM8 (888 ee, 8.8 eeee) eee eeeeeee ee ee eee 8.8 e. Mee eeeeeee eee eeeeeeeee eeee MeMMe. Meeee eeeeee eee eeeeee eeeeeeeeeeeeee (eeeeee eee) eeeeeeeee eee eeeeeee; eeeee: 888 ee (88%); eeeee (M/M) 88:8.
References
[62] | Meee, M.; Meeee, M.; Meeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[63] | Meeee, M. M.; Meeeeee, M. M., Mee. Meee. Mee., (8888) 8, 888. |
[64] | Meee, M.; Meeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |