title: Pd-Catalyzed Conversion of Alkynyl-λ(3)-iodanes to Alkenyl-λ(3)-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation.
abstract: Alkynyl-λ(3)-iodanes have been established as alkynyl cation equivalents for the alkynylation of carbon- and heteroatom-based nucleophiles. Herein, we report an unprecedented reaction mode of this compound class, which features a Pd(II)-assisted 1,2-I(III) shift of an alkynylbenziodoxole. A Pd(II) catalyst mediates this shift and the subsequent interception of the transient vinylidene species with carboxylic acid (1,1-hydrocarboxylation). The product of this stereoselective rearrangement-addition reaction, β-oxyalkenylbenziodoxole, represents a novel and useful building block for further synthetic transformations.
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , Singapore 637371, Singapore.
authors.forename: Junliang
authors.initials: J
authors.lastname: Wu
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , Singapore 637371, Singapore.
authors.forename: Xiaozhou
authors.initials: X
authors.lastname: Deng
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , Singapore 637371, Singapore.
authors.forename: Hajime
authors.initials: H
authors.lastname: Hirao
authors.affiliation: Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , Singapore 637371, Singapore.
authors.forename: Naohiko
authors.initials: N
authors.lastname: Yoshikai