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The Lewis acid mediated reaction of allyltributylstannane compounds with β-hydroxy-α-diazo carbonyls gives β-allyl-α-diazo carbonyl products in good yields. This reaction proceeds via a vinyl diazonium ion intermediate which is intercepted by the allylstannane nucleophile. Importantly, the diazo functional group is retained over the course of the reaction to give diazo-containing scaffolds with increased molecular complexity. Methallyltrimethylsilane also serves as a functional allyl transfer reagent in this reaction.
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A Conjugate Addition Approach to Diazo‐Containing Scaffolds with β Quaternary Centers
Abstract Structurally complex diazo‐containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α‐diazonium‐α,β‐unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β‐hydroxy‐α‐diazo carbonyls with Sc(OTf)3. Conjugate addition occurs selectively at the 3‐position of indole to give α‐diazo‐β‐indole carbonyls, and enoxy silanes react to give 2‐diazo‐1,4‐dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α‐diazo ester indole addition product with Rh2(OAc)4caused a rearrangement to occur to give a 2‐(1H‐indol‐3‐yl)‐2‐enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.
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- Award ID(s):
- 1665113
- PAR ID:
- 10156178
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 59
- Issue:
- 31
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 12827-12831
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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