Atroposelective brominations to access chiral biaryl scaffolds using high-valent Pd-catalysis.

Autor:	Linde ST; Department of Chemistry, Aarhus University DK-8000 Aarhus C Denmark nmr@chem.au.dk., Corti V; Department of Chemistry, Aarhus University DK-8000 Aarhus C Denmark nmr@chem.au.dk., Lauridsen VH; Department of Chemistry, Aarhus University DK-8000 Aarhus C Denmark nmr@chem.au.dk., Lamhauge JN; Department of Chemistry, Aarhus University DK-8000 Aarhus C Denmark nmr@chem.au.dk., Jørgensen KA; Department of Chemistry, Aarhus University DK-8000 Aarhus C Denmark nmr@chem.au.dk., Rezayee NM; Department of Chemistry, Aarhus University DK-8000 Aarhus C Denmark nmr@chem.au.dk.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2023 Mar 03; Vol. 14 (13), pp. 3676-3681. Date of Electronic Publication: 2023 Mar 03 (Print Publication: 2023).
DOI:	10.1039/d2sc06131g
Abstrakt:	Compounds featuring atropisomerism are ubiquitous in natural products, therapeutics, advanced materials, and asymmetric synthesis. However, stereoselective preparation of these compounds presents many synthetic challenges. This article introduces streamlined access to a versatile chiral biaryl template through C-H halogenation reactions employing high-valent Pd catalysis in combination with chiral transient directing groups. This methodology is highly scalable, insensitive to moisture and air, and proceeds, in select cases, with Pd-loadings as low as 1 mol%. Chiral mono-brominated, dibrominated, and bromochloro biaryls are prepared in high yield and excellent stereoselectivity. These serve as remarkable building blocks bearing orthogonal synthetic handles for a gamut of reactions. Empirical studies elucidated regioselective C-H activation to be predicated on the oxidation state of Pd and diverging site-halogenation to result from cooperative effects of Pd and oxidant. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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