Addition Reactions with Formation of Carbon–Oxygen Bonds: (iii) Glycol Forming Reactions

Haines, Alan H.

doi:10.1016/b978-0-08-052349-1.00197-9

Cited by 14 publications

(2 citation statements)

References 62 publications

(19 reference statements)

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“…The protection of the carbonyl group gives the dioxolane 18 , with concomitant isomerization of the double bond in the bicyclic system to the tetrasusbsituted position. Chemoselective oxidation of the side chain of 18 was achieved by treatment with OsO 4 [18,19,20,21], followed by cleavage of the resulting diol with Pb(AcO) 4 to give aldehyde 19 in excellent overall yield (84%) from ent -halimic acid 1 . In this manner we have opened a new and versatile route to intermediate 19 , a key compound for the synthesis of many natural products.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of an ent-Halimanolide from ent-Halimic Acid

et al. 2008

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Section: Resultsmentioning

confidence: 99%

Synthesis of an ent-Halimanolide from ent-Halimic Acid

et al. 2008

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“…Thus the electrochemical conversion of cyclohexene to cyclohexane-1,2-diol appears to be an attractive alternative to chemical conversions with oxygen and catalysts or with hydrogen peroxide [17,[62][63][64][65][66].…”

Section: Electrochemical Conversion Of Cyclohexene (8) To Cyclohexanementioning

confidence: 99%

Cleavage of alkenes by anodic oxidation

Bäumer

Schäfer

2005

J Appl Electrochem

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Oxidative cleavage of olefinic double bonds to carboxylic acids, aldehydes or ketones is one of the important reactions in organic synthesis. Ozonolysis is mostly applied for this purpose, however, high costs for safety precautions in technical scale conversions demand alternatives. For this purpose different electrochemical methods are investigated. In the direct oxidation of cyclohexene at a platinum or graphite anode no cleavage occurs, but substituted and rearranged products are obtained. At the boron doped diamond electrode (BDDE) aliphatic olefins with high oxidation potential are not converted. Electrochemical ozonolysis by oxidation of water to ozone at the lead dioxide electrode leads to carboxylic acids as cleavage products in high material yield but low current yield. Anodic bromo-formyloxylation followed by an anodic cleavage provides a two step conversion of cyclohexene to hexane-1,6-dial derivatives. Thereby anodic discharge of bromide in formic acid leads to (2-bromocyclohexyl)-formate, which is converted to cyclohexane-1,2-diol and the major part of potassium bromide is recovered for the next cycle. This electrochemical conversion appears to be an attractive alternative to chemical oxidations with oxygen and catalysts or with hydrogen peroxide. The diol is cleaved in high yield to hexane-1,6-dial or its acetal either directly or indirectly with periodate as mediator.

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