Synthesis and Characterization of Photoswitchable Dithienylethene-Based Chiral Bisoxazoline Compounds with Bidirectional Visible-Light Control.

In this paper, we have successfully synthesized dithienylethene-based chiral bisoxazoline ligands with bidirectional photoswitching capabilities under visible light irradiation and proposed a strategy for adjusting the conjugation system length in sensitizer groups. The detailed experimental procedures and the characterization data are presented in the main text and the Supporting Information. Despite their moderate photoswitching rates, these ligands provide a promising approach towards developing fully visible light-responsive chiral catalysts.

Visible-light-induced reactions of methylenecyclopropanes (MCPs).

Diverse, visible-light-induced transformations of methylenecyclopropanes (MCPs) have been reported in recent years, attracting significant attention from synthetic chemists. As readily accessible strained molecules, MCPs have sufficient reactivity to selectively generate different target products, through reactions with various radical species upon visible-light irradiation under regulated reaction conditions. These transformations can be classified into three subcategories of reaction pathway, forming ring-opened products, cyclopropane derivatives, and alkynes. These products include pharmaceutical intermediates and polycyclic/heterocyclic compounds that are challenging to obtain using traditional methods. This review summarizes the recent advancements in this field.

The Morita-Baylis-Hillman reaction for non-electron-deficient olefins enabled by photoredox catalysis.

A strategy for overcoming the limitation of the Morita-Baylis-Hillman (MBH) reaction, which is only applicable to electron-deficient olefins, has been achieved via visible-light induced photoredox catalysis in this report. A series of non-electron-deficient olefins underwent the MBH reaction smoothly via a novel photoredox-quinuclidine dual catalysis. The in situ formed key ß-quinuclidinium radical intermediates, derived from the addition of olefins with quinuclidinium radical cations, are used to enable the MBH reaction of non-electron-deficient olefins. On the basis of previous reports, a plausible mechanism is suggested. Mechanistic studies, such as radical probe experiments and density functional theory (DFT) calculations, were also conducted to support our proposed reaction pathways.

Construction of an isoquinolinone framework from carboxylic-ester-directed umpolung ring opening of methylenecyclopropanes.

An interesting type of reaction involving functionalized methylenecyclopropanes (MCPs) has been revealed. Here, a nucleophilic attack of an anionic species onto a partially polarity-reversed MCP was realized by treating a neighbouring carboxylic ester tethered to the MCP and amine with KHMDS to realize an umpolung ring opening of the MCP. This work established an operationally convenient protocol for the rapid construction of isoquinolinone frameworks.

Rapid construction of cyclopenta[b]naphthalene frameworks from propargylic alcohol tethered methylenecyclopropanes.

We have developed a new synthetic methodology for the rapid construction of cyclopenta[b]naphthalene frameworks from the reaction of propargylic alcohol tethered methylenecyclopropanes with mesyl chloride in the presence of triethylamine through cascade cyclization. The reaction can be performed under mild conditions without the use of transition metals, affording the target products in moderate to good yields, and this cyclization reaction process can be scaled up to a gram-scale synthesis.

Lewis or Brønsted acid-catalysed reaction of propargylic alcohol-tethered alkylidenecyclopropanes with indoles and pyrroles for the preparation of polycyclic compounds tethered with indole or pyrrole motif.

We developed a facile synthetic method to access cyclopenta[b]naphthalene derivatives via the Lewis or Brønsted acid catalysed cascade nucleophilic addition, electronic cyclization, ring-opening rearrangement of propargylic alcohol-tethered alkylidenecyclopropanes with indole and pyrrole derivatives. The reaction exhibited a broad substrate scope and good functional group tolerance under metal-free conditions, affording the desired products in moderate to good yields.