Concerning the reactivity of 1,2:3,4-diepoxides towards nucleophiles

Esser, Thomas; Séquin, Urs

doi:10.1016/s0040-4039(00)80506-7

Cited by 7 publications

(3 citation statements)

References 10 publications

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“…In general, vinyloxiranes are known to be regioselectively opened by heteroatom nucleophiles at the allylic position. , In the course of our investigations with oxirane 5 , the lanthanide(III) Lewis acid, ytterbium triflate (Yb(OTf) 3 ), proved to be an efficient and mild catalyst for this transformation (Table ) . Using Yb(OTf) 3 as a catalyst, oxirane 5 could be ring-opened at the allylic position with alcohol, amine, and sulfur nucleophiles in high yields and with good regio- and stereoselectivies.…”

Section: Resultsmentioning

confidence: 93%

“…Indeed, the selective opening of the oxiranes in “ anti -benzene dioxide” ( trans -3,4,5,6-diepoxycyclohexene), derived from p -benzoquinone, has been investigated with various heteroatom nucleophiles resulting in C 2 -symmetric products from bis-S N 2 addition. Alternatively, carbon nucleophiles have been shown to attack in a S N 2‘ fashion, often resulting in less predictable products . In contrast to “ anti -benzene dioxide”, the reactivity of the monooxirane 3 remains little studied; this material is a potential source of unsymmetrical, heavily functionalized cyclohexenyl systems for further elaboration .…”

Section: Introductionmentioning

confidence: 99%

“…In contrast to “ anti -benzene dioxide”, the reactivity of the monooxirane 3 remains little studied; this material is a potential source of unsymmetrical, heavily functionalized cyclohexenyl systems for further elaboration . 4d,5b, …”

Section: Introductionmentioning

confidence: 99%

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Highly Functionalized Cyclohexenyl Systems: Enzymatic Resolution and Selective Oxirane Opening Reactions of p-Benzoquinone Derivatives

Kohrt

Johnson

1998

J. Org. Chem.

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Diol 2, derived in two steps from p-benzoquinone, was converted to epoxy alcohol 3. The latter was resolved with crude Candida rugosa lipase in isopropenyl acetate/toluene to give acetate (−)-4 and residual alcohol (+)-3. Oxirane ring opening reactions of 3 and the corresponding acetate and TBDMS derivatives with a variety of nucleophiles gave diastereomerically pure 3,4,5,6-tetrasubstituted cyclohexene derivatives of type 6. X-ray crystal structures were obtained on compounds 6e, 6m and the diacetate prepared from 6l. Nitrogen nucleophiles provided entry in various aziridines 10. Pd(0)-catalyzed nucleophilic additions to substrate 5 cleanly provided the diastereomeric pattern of type 11. trans-5,6-Disubstituted cyclohexadienes 13 were obtained by an unusual syn-reductive elimination on bromocarbonates 12 utilizing Pd or Zn.

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Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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Highly Functionalized Cyclohexenyl Systems: Enzymatic Resolution and Selective Oxirane Opening Reactions of p-Benzoquinone Derivatives

Kohrt

Johnson

1998

J. Org. Chem.

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Epoxide Migration (Payne Rearrangement) and Related Reactions

Hanson

2002

Organic Reactions

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Under a variety of basic conditions, 2,3‐epoxy alcohols rearrange with inversion at C‐2. The reaction, originally referred to in the literature as the β‐oxanol rearrangement, is now exclusively referred to as epoxide migration or Payne rearrangement. Epoxide migration is reversible, often leading to a mixture of epoxy alcohol isomers. Furthermore, in the presence of hydroxide or other nucleophiles, in situ opening of the equilibrating species may be observed. When such opening is desired, epoxide migration becomes a powerful method for the introduction of functionality into a substrate containing a 2,3‐epoxy alcohol moiety. However, when opening is not desired, epoxide migration can become a significant problem. The epoxide migration process lends itself to other synthetically useful manipulations. For example, the anionic equilibrating species may also be trapped with electrophiles such as alkyl and silyl halides, alkyl sulfonates, and epoxides. Electrophilic trapping may be inter‐ or intramolecular, and has been used as a means of delivering functionality to either C‐2 or C‐3 selectively. The intent of this chapter is to provide a comprehensive review of epoxide migration, including factors influencing the equilibrium position, conditions leading to in situ epoxide opening, and examples of electrophilic trapping. The reaction is discussed in relation to its utility as a synthetic method as well as its prevention as an unwanted side reaction. Related rearrangements in which either the epoxide or hydroxy oxygen has been replaced with nitrogen or sulfur have also been studied. These reactions, referred to in the literature as aza‐Payne and thia‐Payne rearrangements, respectively, are comprehensively included in this chapter as well. For the purposes of this discussion, the term “forward” aza‐Payne rearrangement refers to the direction of reaction leading from oxirane to aziridine. Similarly, “forward” thia‐Payne rearrangement refers to the direction of reaction leading from oxirane to thiirane. In the case of aza‐Payne rearrangements, both forward and reverse reactions have been effected, and in this chapter the term “reverse” aza‐Payne rearrangement refers to reactions leading from aziridine to oxirane. Epoxides have long been considered important in the chemistry of carbohydrates, and epoxide migration in the context of carbohydrate chemistry has been discussed in several reviews. In addition, particularly since discovery of the catalytic asymmetric epoxidation of allylic alcohols and the rise in importance of enantiomerically enriched acyclic epoxy alcohols, epoxide migration with in situ opening in acyclic systems has been much studied. The tabular survey summarizes the literature of epoxide migration and related reactions, including equilibration, in situ opening and trapping, aza‐Payne rearrangements, and thia‐Payne rearrangements, from 1931 to 1999. Reports referring to reactions involving addition at C‐1 or C‐3 without inversion of stereochemistry at C‐2 as “Payne rearrangements” are not covered in this review.

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Isomerization of Alkenes

Larock

Zeni

2018

Comprehensive Organic Transformations

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Alkene Inversion Simple Rearrangement Functional Group Rearrangement Reductive Transposition Oxidative Transposition Metal and Heteroatom Displacement Ene Reaction Alkylative Transposition

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Concerning the reactivity of 1,2:3,4-diepoxides towards nucleophiles

Cited by 7 publications

References 10 publications

Highly Functionalized Cyclohexenyl Systems: Enzymatic Resolution and Selective Oxirane Opening Reactions of p-Benzoquinone Derivatives

Highly Functionalized Cyclohexenyl Systems: Enzymatic Resolution and Selective Oxirane Opening Reactions of p-Benzoquinone Derivatives

Epoxide Migration (Payne Rearrangement) and Related Reactions

Isomerization of Alkenes

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