1829-26-1Relevant articles and documents
Tosyloxybenziodoxolone: A Platform for Performing the Umpolung of Alkynes in One-Pot Transformations
Borrel, Julien,Waser, Jerome
supporting information, (2021/12/27)
Ethynylbenziodoxolones (EBXs) are commonly encountered reagents for the electrophilic alkynylation of nucleophiles. Herein, we report a one-pot, two-step process for EBX generation and their direct application in substrate functionalization. Our approach enables us to bypass the originally mandatory isolation and purification of the reagents, resulting in a more efficient synthesis. We could apply this process to seven different transformations involving both two- and one-electron nucleophiles to obtain a large variety of alkynylated products.
Practical synthesis of 2-iodosobenzoic acid (IBA) without contamination by hazardous 2-iodoxybenzoic acid (IBX) under mild conditions
China, Hideyasu,Dohi, Toshifumi,Kageyama, Nami,Takenaga, Naoko,Yatabe, Hotaka
, (2021/06/18)
We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.
Site Selective Chlorination of C(sp3)?H Bonds Suitable for Late-Stage Functionalization
Fawcett, Alexander,Keller, M. Josephine,Herrera, Zachary,Hartwig, John F.
, p. 8276 - 8283 (2021/03/15)
C(sp3)?Cl bonds are present in numerous biologically active small molecules, and an ideal route for their preparation is by the chlorination of a C(sp3)?H bond. However, most current methods for the chlorination of C(sp3)?H bonds are insufficiently site selective and tolerant of functional groups to be applicable to the late-stage functionalization of complex molecules. We report a method for the highly selective chlorination of tertiary and benzylic C(sp3)?H bonds to produce the corresponding chlorides, generally in high yields. The reaction occurs with a mixture of an azidoiodinane, which generates a selective H-atom abstractor under mild conditions, and a readily-accessible and inexpensive copper(II) chloride complex, which efficiently transfers a chlorine atom. The reaction's exceptional functional group tolerance is demonstrated by the chlorination of >30 diversely functionalized substrates and the late-stage chlorination of a dozen derivatives of natural products and active pharmaceutical ingredients.