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. 2024 Oct 18;89(20):15352-15357.
doi: 10.1021/acs.joc.4c01886. Epub 2024 Oct 10.

Taming Tethered Nitreniums for Alkene Functionalization Reactions

Raju Silver  1 , Appasaheb K Nirpal  1 , Shyam Sathyamoorthi  1
Affiliations

Taming Tethered Nitreniums for Alkene Functionalization Reactions

Raju Silver et al. J Org Chem. .

Abstract

We present the first examples of amino-trifluoroacetoxylations of alkenes using N-alkoxy carbamate tethers. Hypervalent iodine oxidants mediate this transformation, providing a "green" alternative to existing intramolecular amino-hydroxylation protocols which use toxic metals such as osmium. In all cases examined, the reaction is regioselective and stereospecific, with the geometry of the starting alkene controlling the diastereomeric outcome. By analogy to prior art and from our own observations, we posit that a transient nitrenium species serves as a key intermediate.

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Figures

Scheme 1.
Scheme 1.
Existing reports of intramolecular alkene functionalization reactions with nitreniums have employed amines or amides. We present the first examples of using "tethered" nitreniums with removable auxiliaries attached to alcohols.
Scheme 2.
Scheme 2.
Structure-Reactivity Relationship with Nitrenium Tethers.
Scheme 3.
Scheme 3.
Alkene scope and functional group compatibility.
Scheme 4.
Scheme 4.
Poor Performers.
Scheme 5.
Scheme 5.
(A) Putative reaction mechanism. (B) Indirect evidence of nitrenium formation.
Scheme 6.
Scheme 6.
(A) Scale up. (B) Applications.
See this image and copyright information in PMC

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