An aza-Payne rearrangement-epoxide ring opening reaction of 2-aziridinemethanols in a one-pot manner: A regio- and stereoselective synthetic route to diastereomerically pure N-protected 1,2-amino alcohols

Ibuka, Toshiro; Nakai, Kengo; Akaji, Masako; Tamamura, Hirokazu; Fujii, Nobutaka; Yamamoto, Yoshinori

doi:10.1016/0040-4020(96)00682-5

Cited by 27 publications

(11 citation statements)

References 52 publications

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“…It should be clearly noted that the use of MeLi•LiBr or MeMgBr instead of Me 2 Cu(CN)Li 2 •2LiBr did not result in clean transformations. 35 The usefulness of this one-flask reaction would be enhanced if it could be successfully extended to other nucleophiles. Alkylthio and arylthio groups are important functional groups in various types of chemical transformations and, as shown in Scheme 22, the reactions of 25 and 70 with KH followed by PhSH in a one-pot manner gave the diastereomerically pure phenylthio amino alcohols 132 and 133 in 92 and 89% yields, respectively.…”

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

“…Although similar treatment with KH and Bu t SH yielded only the corresponding tert-butylthio amino alcohols, the overall yields of products were considerably lower (60-70%). 35 N-Protected 1,2-amino alcohols bearing a nitrile group could also be prepared in a one-pot manner as shown in Scheme 23. The reaction of 70 and 135 with KH followed by the sequential addition of Me 3 SiCN (3 equiv.)…”

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

“…This reaction also appears to be quite general, giving yields which are good to excellent. 35 As shown in Scheme 24, synthesis of diamino alcohols 137 and 138 from aziridines 29 and 70 was also investigated. All attempts to use either dibenzylamine or lithium dibenzylamide to effect the epoxide ring opening of an anionic intermediate derived from 2-aziridinemethanol 29 were unsuccessful.…”

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

“…For example, (2R,3S)-C18-dihydrosphingosine 140 can be readily synthesized in good overall yields from 2-aziridinemethanol 135 as shown in Scheme 25 via a sequence of reactions. 35…”

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

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The aza-Payne rearrangement: a synthetically valuable equilibration

Ibuka¹

1998

Chem. Soc. Rev.

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135

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Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

“…For example, (2R,3S)-C18-dihydrosphingosine 140 can be readily synthesized in good overall yields from 2-aziridinemethanol 135 as shown in Scheme 25 via a sequence of reactions. 35…”

Section: Aza-payne Rearrangement Reaction Of 23-epoxy Aminesmentioning

confidence: 99%

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The aza-Payne rearrangement: a synthetically valuable equilibration

Ibuka¹

1998

Chem. Soc. Rev.

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135

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“…AZACYCLOALKANES FROM EPOXIDES AND AZIRIDINES[254][255][256]. The isomerization of epoxyamines 294 into the corresponding 2-trimethylsiloxymethylaziridinium ions 295 induced by Lewis acids was described; the intermediates were characterized applying 1 H NMR spectroscopy.…”

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Azacycloalkanes from epoxides and aziridines

2011

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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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An aza-Payne rearrangement-epoxide ring opening reaction of 2-aziridinemethanols in a one-pot manner: A regio- and stereoselective synthetic route to diastereomerically pure N-protected 1,2-amino alcohols

Cited by 27 publications

References 52 publications

The aza-Payne rearrangement: a synthetically valuable equilibration

The aza-Payne rearrangement: a synthetically valuable equilibration

Azacycloalkanes from epoxides and aziridines

Epoxide Migration (Payne Rearrangement) and Related Reactions

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