A new method for beta-phenol annulation involving base-induced [4C + 2C] cycloaromatization of readily available 4-bis(methylthio)-3-buten-2-one with a variety of cyclic and acyclic active methylene ketones has been reported. Appropriate choice of ketones allows synthesis of diverse frameworks such as dihydroindan, tetrahydronaphthalenes, their higher homologues, dihydro/octahydrophenanthrenes, anthracene, and heteroannulated analogue in high yields with regiocontrol of phenolic functionality.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/jo020219r | DOI Listing |
Nat Commun
January 2025
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China.
(Hetero)polyaryl amines are extensively prevalent in pharmaceuticals, fine chemicals, and materials but the intricate and varied nature of their structures severely restricts their synthesis. Here, we present a selective multicomponent cycloaromatization of structurally and functionally diverse amine substrates for the general and modular synthesis of (hetero)polyaryl amines through copper(I)-catalysis. This strategy directly constructs a remarkable range of amino group-functionalized (hetero)polyaryl frameworks (194 examples), including naphthalene, binaphthalene, phenanthren, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, quinoline, isoquinoline, quinazoline, and others, which are challenging or impossible to obtain using alternative methods.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Chile.
This paper presents a theoretical study on the distinguishable regiodivergent C-C Myers-Saito and C-C Schmittel routes of benzannelated enyne-allene cycloaromatizations, in which substitutions on the terminal alkyne by alkyl (-CH, -CHCH, -CH(CH) and -C(CH)) and aryl (-CH and -CH(CH)) groups were included. Mechanistic differences were found between substituents attached to alkynes with and without α-H, whereas in the former the Schmittel cyclization proceeds together with 1,8-H migration, in the latter it does so as the sole primitive event. It was also observed that bulky substituents preferentially favor the C-C Schmittel route, and the statistical prediction of regioselectivity is greatly affected when the ratio of accessible vibrational microstates of the transition states is included, especially in highly competing routes, , ΔΔ → 0.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, Indiana University Bloomington IN 47405 USA
Small
November 2024
IMDEA Nanoscience, C/ Faraday 9, Campus de Cantoblanco, Madrid, 28049, Spain.
The synthesis of porphyrinoid-based low-dimensional polymers has recently attracted considerable interest in view of their intriguing electronic, optical, and catalytic properties. Here, this is introduced by the surface-assisted synthesis of two carbaporphyrinoid-based polymers of increasing dimensionality under ultrahigh-vacuum conditions. The structural and electronic characterization of the resulting polymers has been performed by scanning tunneling and non-contact atomic force microscopies, complemented by theoretical modeling.
View Article and Find Full Text PDFOrg Lett
October 2024
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education), and Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, Hunan Normal University, Changsha, Hunan 410081, China.
Herein, a palladium-catalyzed bicycloaromatization of -(alkynyl)styrenes with alkynes is reported. In this protocol, the 6-- cyclization of -(alkynyl)styrenes is followed by deprotonation to complete the first cycloaromatization, and then, a regioselective alkyne insertion/C-H activation occurs to achieve the second cycloaromatization, resulting in atom- and step-economical syntheses of polysubstituted chrysenes. Notably, the products can be further used to construct π-extended arenes using the Scholl reaction.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!