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. 2012 Mar 16;14(6):1386-9.
doi: 10.1021/ol300063t. Epub 2012 Feb 24.

Sequential allylic C-H amination/vinylic C-H arylation: a strategy for unnatural amino acid synthesis from α-olefins

Chao Jiang  1 , Dustin J Covell, Antonia F Stepan, Mark S Plummer, M Christina White
Affiliations

Sequential allylic C-H amination/vinylic C-H arylation: a strategy for unnatural amino acid synthesis from α-olefins

Chao Jiang et al. Org Lett. .

Abstract

Tandem reaction sequences that selectively convert multiple C-H bonds of abundant hydrocarbon feedstocks to functionalized materials enable rapid buildup of molecular complexity in an economical way. A tandem C-H amination/vinylic C-H arylation reaction sequence is described under Pd(II)/sulfoxide-catalysis that furnishes a wide range of α- and β-homophenylalanine precursors from commodity α-olefins and readily available aryl boronic acids. General routes to enantiopure amino acid esters and densely functionalized homophenylalanine derivatives are demonstrated.

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Figures

Scheme 1
Scheme 1. A C—H Amination Route to Homophenylalanines
a PhBQ = phenyl-benzoquinone, b BisSO ligand = 1,2 bis(phenyl-sulfinyl)ethane (Ref. 3b and 3e).
Scheme 2
Scheme 2. Scope of the Sequential Allylic C—H Amination/Vinylic C—H Arylation Reaction
Yields reported are isolated, and the average of at least 2 independent runs. All products were isolated as a single region and olefin E:Z isomer.
Scheme 3
Scheme 3. Sequential Allylic C—H Amination/Vinylic C—H Arylation Reaction toward β-Amino Acid Motif
a Additives: p-nitrobenzoic acid (10 mol %), BisSO ligand (5 mol %).
Scheme 4
Scheme 4. Synthesis of Enantiopure Homophenylalanine Derivative
Scheme 5
Scheme 5. Access to Functionalized Homophenylalanine Derivatives through Sharpless Asymmetric Dihydroxylation
See this image and copyright information in PMC

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