Total synthesis of 2,6-epoxy-2H-1-benzoxocin sugar analogs

Hauser, Frank M.; Ellenberger, William P.; Adams, Theodore C.

doi:10.1021/jo00181a004

Cited by 13 publications

(3 citation statements)

References 2 publications

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“…95 Hauser et al reported an even more remarkable case of differential reactivity of sulfoxide diastereomers in which, whereas 117 rearranged smoothly to allylic alcohol 118, the other sulfoxide diastereomer was completely unreactive, presumably because of the severe interactions between Ph and Me groups in the geometry necessary for a successful rearrangement. 96 The Mislow−Braverman−Evans rearrangement of γ-chloroallyl sulfoxides takes place much faster than the rearrangement of the nonhalogenated counterparts and produces α,βunsaturated ketones in good yields if the process is carried out with cyclohexene as a PhSCl trap. 97 This allows for a completely chemoselective rearrangement of bis-sulfoxide 119 to unsaturated keto sulfoxide 120 in excellent yield, along with 121 through intermediate 122 (Scheme 22).…”

Section: From Allyl Sulfoxidesmentioning

confidence: 99%

“…In contrast, the rapidly reacting diastereomer at sulfur would place the Ph moiety far from the tertiary alcohol . Hauser et al reported an even more remarkable case of differential reactivity of sulfoxide diastereomers in which, whereas 117 rearranged smoothly to allylic alcohol 118 , the other sulfoxide diastereomer was completely unreactive, presumably because of the severe interactions between Ph and Me groups in the geometry necessary for a successful rearrangement …”

Section: General Scope Of [23]-sigmatropic Sulfoxide–sulfenate Rearra...mentioning

confidence: 99%

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From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

et al. 2017

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The [2,3]-sigmatropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally shifted toward the sulfoxide. In the presence of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions. In most cases, a good transfer of stereochemical information through an ordered transition state is obtained. Furthermore, the ease of coupling this process with other versatile, stereocontrolled reactions has enhanced the usefulness of this protocol. This review aims to provide a comprehensive survey of this rearrangement and its application in the synthesis of natural and bioactive products.

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Section: From Allyl Sulfoxidesmentioning

confidence: 99%

Section: General Scope Of [23]-sigmatropic Sulfoxide–sulfenate Rearra...mentioning

confidence: 99%

From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

et al. 2017

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“…Heating the 7.7:1 mixture of adducts 8 and 9 in refluxing toluene induced a [2,3]-sigmatropic rearrangement, giving thiadiazolidines 10 and 11 in a 7.7:1 ratio in quantitative yield. We have previously shown that this type of rearrangement is stereospecific, with isomers having the stereochemistry shown in 8 affording 10 and 9 giving ll.4•5…”

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confidence: 99%