Asymmetric Cycloaddition Reactions of Aryne Intermediates with a Chiral Carbon–Carbon Axis: Syntheses of Axially Chiral Biaryl Compounds

Yoshimura, Tomoyuki; Onda, Ken-ichi; Matsuo, Jun-ichi

doi:10.1021/acs.orglett.3c03983

Cited by 1 publication

(1 citation statement)

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“…Arynes are remarkably versatile electrophiles able to accept a huge variety of functional groups to two neighboring aromatic carbons in a single procedure. 54 Accordingly, arynes have secured roles as key intermediates in the syntheses of natural products, 55 biaryl systems, 56 polycyclic aromatic hydrocarbons, 57 and beyond. 58 A variety of methods for the generation of arynes has been reported, 59 including deprotonation ortho to the I(III) center of diaryliodonium salts, 59b , 60 which is mild and operationally simple.…”

Section: Resultsmentioning

confidence: 99%

Derivatization of 2,1,3-Benzothiadiazole via Regioselective C–H Functionalization and Aryne Reactivity

Kunz,

Barnå,

Urrutia

et al. 2024

J. Org. Chem.

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Despite growing interest in 2,1,3-benzothiadiazole (BTD) as an integral component of many functional molecules, methods for the functionalization of its benzenoid ring have remained limited, and many even simply decorated BTDs have required de novo synthesis. We show that regioselective Ir-catalyzed C−H borylation allows access to versatile 5-boryl or 4,6-diboryl BTD building blocks, which undergo functionalization at the C4, C5, C6, and C7 positions. The optimization and regioselectivity of C−H borylation are discussed. A broad reaction scope is presented, encompassing ipso substitution at the C−B bond, the first examples of ortho-directed C−H functionalization of BTD, ring closing reactions to generate fused ring systems, as well as the generation and capture reactions of novel BTD-based heteroarynes. The regioselectivity of the latter is discussed with reference to the Aryne Distortion Model.

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