1998
DOI: 10.1021/ja980916u
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Regioselective Intramolecular Oxidation of Unactivated C−H Bonds by Dioxiranes Generated in Situ

Abstract: Regioselective oxidation of unactivated C-H bonds has been a challenging problem in organic synthesis. 1,2 Intramolecular oxidation, due to its geometric constraint, has become a very effective approach. In particular, significant progress has been made in remote oxidation of rigid substrates such as steroids. 3,4a,b For flexible substrates, selective oxidation of remote carbons four bonds away from a heteroatom has been successfully achieved by using the radical reactions that undergo intramolecular radica… Show more

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Cited by 82 publications
(49 citation statements)
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“…Specifically, chemists have long used the distance limitations inherent in intramolecular reactions to control the regioselectivity of CH functionalization reactions 6–9. Unfortunately, these concepts are also limited by weak activation interactions6 or are dependent on irregular directing‐group effects within the carbon framework 7a…”
Section: Methodsmentioning
confidence: 99%
“…Specifically, chemists have long used the distance limitations inherent in intramolecular reactions to control the regioselectivity of CH functionalization reactions 6–9. Unfortunately, these concepts are also limited by weak activation interactions6 or are dependent on irregular directing‐group effects within the carbon framework 7a…”
Section: Methodsmentioning
confidence: 99%
“…4 Examples of stoichiometric C-H hydroxylation using these oxidants, as detailed in the following paragraphs, has led to a longstanding interest in expanding their catalytic use to C-H functionalization. 5 Figure 1 Previous work: Heterocyclic oxidants as reagents for C(sp 3 )-H oxidation The use of dioxiranes as reagents for selective C-H hydroxylation has been investigated as far back as the 1980's. Initially, the successful isolation of purified dimethyldioxirane (DMDO) allowed Murray to investigate its reactivity, which led to the discovery of its ability to convert alkanes into the corresponding alcohols at room temperature via stereospecific O-atom insertion.…”
Section: Background: C-h Oxidation Capabilities Of Heterocyclic Oxidantsmentioning
confidence: 99%
“…Dioxirane generated in situ from 1,1,1-triuoroacetone and Oxone was used as the oxidizing agent. [48][49][50][51][52][53][54][55][56][57][58][59] Initially, the reaction was carried out at room temperature by stirring trans-1,4-dimethylcyclohexane (1) (1.0 mmol) with b-CD (1.1 mmol) and 1,1,1-triuoroacetone (1.0 mmol) in water (50 mL) for 1 h, and then 8 portions of a mixture of Oxone (2.5 mmol  8) and NaHCO 3 (7.75 mmol  8) were added within 7 h (one portion was added per hour). Aer stirring for an additional 16 h, the hydroxylation product 1a was isolated in 12% yield by ash column chromatography (Table 1, entry 1).…”
Section: The Effect Of Different Cds On C-h Bond Hydroxylation Of Cycmentioning
confidence: 99%