Functionalizing specific positions on a saturated alkyl molecule is a key challenge in synthetic chemistry. Herein, a ligand-controlled regiodivergent alkylations of alkyl bromides at different positions by Ni-catalyzed alkyl-alkyl cross-electrophile coupling with the second alkyl bromides has been developed. The reaction undergoes site-selective isomerization on one alkyl bromides in a controlled manner, providing switchable access to diverse alkylated structures at different sites of alkyl bromides. The reaction occurs at three similar positions with excellent chemo-and regioselectivity, representing a remarkable ligand tuned reactivity between alkyl-alkyl cross-coupling and nickel migration along the hydrocarbon side chain. This reaction offers a catalytic platform to diverse saturated architectures by alkyl-alkyl bond-formation from identical starting materials.
Phenols are ubiquitous substructures in natural products and bioactive compounds. However, practical methods for the direct construction of phenols under mild conditions remains challenging. Herein, a photocatalytic acceptorless dehydrogenative aromatization of cyclohexanones or cyclohexenones at room temperature has been developed. The reaction features the visible-light and cobalt co-catalyzed sequential dehydrogenation of in-situ formed enol silyl ethers, which are regarded as a challenging process. This operationally simple method enables a series of phenols with diverse substitution patterns from cyclohexanones or cyclohexenones, providing a general and straightforward method for the synthesis of phenols from simple starting materials under mild conditions.
Functionalizing specific positions on a saturated alkyl molecule is a key challenge in synthetic chemistry. Herein, a ligand-controlled regiodivergent alkylations of alkyl bromides at different positions by Ni-catalyzed alkyl-alkyl cross-electrophile coupling with the second alkyl bromides has been developed. The reaction undergoes site-selective isomerization on one alkyl bromides in a controlled manner, providing switchable access to diverse alkylated structures at different sites of alkyl bromides. The reaction occurs at three similar positions with excellent chemo-and regioselectivity, representing a remarkable ligand tuned reactivity between alkyl-alkyl cross-coupling and nickel migration along the hydrocarbon side chain. This reaction offers a catalytic platform to diverse saturated architectures by alkyl-alkyl bond-formation from identical starting materials.
Phenols are ubiquitous substructures in natural products and bioactive
compounds. However, practical methods for the direct construction of
phenols under mild conditions remains challenging. Herein, a
photocatalytic acceptorless dehydrogenative aro-matization of
cyclohexanones or cyclohexenones at room temperature has been developed.
The reaction features the visible-light and cobalt co-catalyzed
sequential dehydrogenation of in-situ formed enol silyl ethers, which
are regarded as a challenging process. This operationally simple method
enables the synthesis of a series of phenols with diverse substitution
patterns from cyclohexanones or cyclohexenones. Moreover, diverse
substituted 1,2-, 1,3-, and 1,4-benzenediols were obtained from
cyclo-hexanediones, providing a general and straightforward method for
the synthesis of phenols from simple starting materials un-der mild
conditions
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.