Regiochemical Effect of an α-Trimethylsilyl Group on Epoxide Reactions with Non-nucleophilic Bases

Hudrlik, Paul F.; Tafesse, and Laykea; Hudrlik, Anne M.

doi:10.1021/ja972256j

Cited by 10 publications

(5 citation statements)

References 15 publications

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“…[α] D 20 +33.4 (c = 1.2, chloroform); HPLC (Chiralcel OD–H) 5:95 i -PrOH/Hexane, 1.0 mL/minute, λ = 220 nm, t minor = 6.9 min, t major = 8.4 min, ee = 92.4%. The characterization data for compound ( S )-1p are comparable with that of a previous report …”

Section: Methodssupporting

confidence: 85%

“…The characterization data for compound (S)-1p are comparable with that of a previous report. 20 1,3-Rearrangement of (S)-1p. To a round-bottom flask (50 mL) containing the substrate (S)-1p (190 mg, 1 mmol, 92.4% ee) was added 1,4-dioxane (2.5 mL), and then to the solution was added H 2 O (22.5 mL).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…White solid: mp = 94−96 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.37−7.26 (m, 4H), 6.72 (dd, J = 15.6, 10.5 Hz, 1H), 6.49 (d, J = 15.7 Hz, 1H), 6.36 (dd, J = 15.2, 10.5 Hz, 1H), 5.88 (dd, J = 15.2, 6.3 Hz, 1H), 4.50−4.35 (m, 1H), 1.57 (br s, 1H), 1.33 (d, J = 6.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 138. 3, 135.7, 133.1, 131.3, 129.4, 128.8, 128.8, 127.5, 68.5, 23.3; MS (EI, 70 eV) m/z (%) 208 (M + , 24), 190 (20), 151 (20), 125 (70), 77 (11), 43 (100); HRMS (EI) for C 12 H 13 ClO calcd for [M] + m/z 208.0655, found 208.0648.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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1,n-Rearrangement of Allylic Alcohols Promoted by Hot Water: Application to the Synthesis of Navenone B, a Polyene Natural Product

Wang

2014

J. Org. Chem.

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It was reported for the first time that hot water as a mildly acidic catalyst efficiently promoted 1,n-rearrangement (n = 3, 5, 7, 9) of allylic alcohols. In some cases, the rearrangement reactions joined isolated C-C double or triple bonds to generate conjugated polyene or enyne structure motifs. We used the 1,3-rearrangement reaction of an allylic alcohol in hot water as part of an attractive new strategy for construction of the polyene natural product navenone B by iterative use of a Grignard reaction, a 1,3-rearrangement of the resulting allylic alcohol, and subsequent oxidation of the rearranged product.

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Section: Methodssupporting

confidence: 85%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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1,n-Rearrangement of Allylic Alcohols Promoted by Hot Water: Application to the Synthesis of Navenone B, a Polyene Natural Product

Wang

2014

J. Org. Chem.

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“…Proteodesilylation of α-hydroxy silylenones12,13 and site-selective eliminative opening of silyl substituted epoxides are known 14,15. We examined this type of elimination for spirodiepoxides derived from 5 , 14 and 15 (Table 2).…”

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confidence: 99%

“…Encouraged by the above results, we set out to realize the eliminative opening of spirodiepoxides ( XIV → XVII , Scheme ). Proteodesilylation of α-hydroxy silyl enones , and site-selective eliminative opening of silyl-substituted epoxides are known. , We examined this type of elimination for spirodiepoxides derived from 5 , 14 , and 15 (Table ). Brønsted and Lewis acids in polar solvent were found to effect enone formation (entries 1−3).…”

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confidence: 99%