Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition
An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Br?nsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with
Pattillo, Christopher C.,Strambeanu, Iulia I.,Calleja, Pilar,Vermeulen, Nicolaas A.,Mizuno, Tomokazu,White, M. Christina
supporting information
p. 1265 - 1272
(2016/02/18)
Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis
A novel heterobimetallic Pd(II)sulfoxide/(salen)Cr(III)Cl-catalyzed intermolecular linear allylic C-H amination (LAA) is reported. This reaction directly converts densely functionalized α-olefin substrates (1 equiv) to linear (E)-allylic carbamates with good yields and outstanding regio- and stereoselectivities (>20:1). Chiral bis-homoallylic and homoallylic oxygen, nitrogen, and carbon substituted α-olefins undergo allylic C-H amination with good yields, excellent selectivities, and no erosion in enantiomeric purity. Streamlined routes to (E)-allylic carbamates that can be further elaborated to medicinally and biologically relevant allylic amines are also demonstrated. Valuable 15N-labeled allylic amines may be generated directly from allyl moieties at late stages of synthetic routes by using the readily available 15N-(methoxycarbonyl)-p-toluenesulfonamide nucleophile. Evidence is provided that this reaction proceeds via a heterobimetallic mechanism where Pd/sulfoxide mediates allylic C-H cleavage to form a π-allylPd intermediate, and (salen)Cr(III)Cl/BQ work together to promote functionalization with the nitrogen nucleophile. Copyright
Reed, Sean A.,White, M. Christina
p. 3316 - 3318
(2008/10/09)
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