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5.2.1.4.1 Rearrangement of Allyl Sulfoxides

DOI: 10.1055/sos-SD-206-00325

Fringuelli, F.; Piermatti, O.Science of Synthesis: Water in Organic Synthesis, (20121496.

[2,3]-Sigmatropic rearrangement of allyl sulfoxides (MislowEvans 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.

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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]

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(M)-8-Meeeeeeeee-8-eeee [88, M8=(MM8)8Me; M8=M8=M8=M]; Meeeeee Meeeeeeee:[‌88‌]

M eeeee eeee ee eeeeeee/M8M (8:8; 8eM) eeeeeeeeee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-ee-8-ee [88, M8=(MM8)8Me; M8=M8=M8=M; M8=Me; 888ee, 8.88eeee] eee MeMM8 (888ee, 8.8eeee) eee eeeeeee ee ee eee 8.8e. Mee eeeeeee eee eeeeeeeee eeee MeMMe. Meeee eeeeee eee eeeeee eeeeeeeeeeeeee (eeeeee eee) eeeeeeeee eee eeeeeee; eeeee: 888ee (88%); eeeee (M/M) 88:8.

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