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Volumn , Issue 12, 2008, Pages 1785-1788

Lewis acid promoted oxidative rearrangement of tertiary allylic alcohols with the PhIO/TEMPO system

Author keywords

Iodosylbenzene; Lewis acids; Oxidation; TEMPO; Tertiary allylic alcohols

Indexed keywords

ALLYL ALCOHOL; BISMUTH TRIFLATE; CYCLOHEXENE DERIVATIVE; LEWIS ACID; PHIO1 BUTYL 2 CYCLOHEXEN 1 OL; TRIFLUOROMETHANESULFONIC ACID;

EID: 48349142861     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1078500     Document Type: Article
Times cited : (38)

References (55)
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    • General Procedure for Lewis Acid Catalyzed Oxidative Rearrangement of Tertiary Allylic Alcohols with TEMPO and PhIO (Table 2) To a solution of tertiary alcohol (1 mmol) in CH2Cl2 (5 mL) were added PhIO (264 mg, 2 equiv) and TEMPO (15.6 mg, 0.1 equiv, For method B and C, powdered 4 Å MS was also added (0.08 and 0.13 g/mmol, respectively, The suspension was cooled to 0°C and Lewis acid was added. Dissolution of PhIO is indicative of the end of the reaction. For method A, just after dissolution of PhIO, powdered NaHCO3 was added and the stirring was continued for 10 min. In all cases, the reaction was poured onto a column of SiO2 (20 g) and eluted with EtOAc-PE 1:6, The purity of each synthesized carbonyl compound was checked by NMR spectroscopy
    • 2 (20 g) and eluted with EtOAc-PE (1:6). The purity of each synthesized carbonyl compound was checked by NMR spectroscopy.
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    • We have shown that allylic alcohols are rapidly oxidized, at 0°C, with TEMPO/PhIO/Yb(OTf)3 system, see ref. 6b
    • 3 system, see ref. 6b.
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    • Strong protic acids are known to depolymerize PhIO, see ref. 17b.
    • Strong protic acids are known to depolymerize PhIO, see ref. 17b.
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    • 2. After 15 min, it was observed by TLC the disappearance of the starting material and formation of UV-absorbing, nonpolar products (dehydrated products).
    • 2. After 15 min, it was observed by TLC the disappearance of the starting material and formation of UV-absorbing, nonpolar products (dehydrated products).


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