Brønsted Acid-Catalyzed Intramolecular Tandem Double Cyclization of γ-Hydroxy Acetylenic Ketones with Alkynes into Naphtho[1,2-b]furan-3-ones.

A metal-free and atom-economic route for the synthesis of naphtho[1,2-b]furan-3-ones has been realized via p-TsOH·H2O-catalyzed intramolecular tandem double cyclization of γ-hydroxy acetylenic ketones with alkynes in formic acid. The benzene-linked furanonyl-ynes are the key intermediates obtained by the scission/recombination of C-O double bonds. Further, the structural modifications of the representative product were implemented by reduction, demethylation, substitution, and [5 + 2]-cycloaddition.

Dual Proton/Silver-Catalyzed Serial (5 + 2)-Cycloaddition and Nazarov Cyclization of (E)-2-Arylidene-3-hydroxyindanones with Conjugated Eneynes: Synthesis of Indanone-Fused Benzo[cd]azulenes.

A one-pot step-economic tandem process involving (5 + 2)-cycloaddition and Nazarov cyclization reactions has been reported for the facile synthesis of indanone-fused benzo[cd]azulenes from (E)-2-arylidene-3-hydroxyindanones and conjugated eneynes. This highly regio- and stereoselective bisannulation reaction is enabled by dual silver and Brønsted acid catalysis and opens up a new avenue for the construction of important bicyclo[5.3.0]decane skeletons.

Metal-Free Intramolecular [3+2] Cycloaddition of γ-Hydroxy Acetylenic Ketones with Alkynes for the Synthesis of Naphtho[1,2-c]furan-5-ones and Its Derivatization via a Selective C(sp2)-H Deuteration Reaction.

A metal-free intramolecular [3+2] cycloaddtion has been achieved by treating benzene-linked propynol-ynes with AcOH/H2O in a one-pot manner. The reaction provides greener, 100% atom-economic, highly regioselective, and more practical access to functionalized naphtho[1,2-c]furan-5-ones with valuable and versatile applications. The regioselective α-deuteration of naphtho[1,2-c]furan-5-ones has been also presented with excellent deuterium incorporation and chemical yields. Moreover, the fluorescent properties of naphtho[1,2-c]furan-5-one products have been investigated in solution.

Brønsted-Acid-Catalyzed Synthesis of 3-Alkoxy and 3-Sulfamido Indanones via a Tandem Cyclization.

Brønsted-acid-catalyzed allylic substitution reactions of the in situ generated 3-hydroxy indanones with alcohols and sulfamides were investigated, which provided a facile route for the synthesis of a large variety of 3-alkoxy and 3-sulfamido indanones. The key intermediates, 3-hydroxy indanones, were obtained through the intramolecular Meyer-Schuster rearrangement of o-propargyl alcohol benzaldehydes. The resulting 3-benzyloxy indanone could be selectively modified by allylic sulfonamidation and reduction reactions.

Recent developments in the group-1B-metal-catalyzed synthesis of pyrroles.

Pyrroles are important synthetic targets as a result of their occurrence in numerous biologically active molecules, their important roles in diverse living processes, and their utility as versatile intermediates. As a consequence, numerous efforts focused on the development of concise and efficient methods for the construction of pyrroles. Compared with other transition metals, the group 1B metals (Cu, Ag and Au) are probably more versatile and widely used for the synthesis of pyrroles in organic chemistry. Considering the importance of both topics in organic synthesis, here we summarize recent achievements in the synthesis of pyrroles catalyzed by monometallic systems which belong to the group 1B metals (Cu, Ag and Au).

Carbamates of 4'-demethyl-4-deoxypodophyllotoxin: synthesis, cytotoxicity and cell cycle effects.

In an attempt to generate compounds with superior bioactivity and reduced toxicity, 12 carbamates of 4'-demethyl-4-deoxypodophyllotoxin, N-(1-oxyl-4'-demethyl- 4-deoxypodophyllic)-α-amino acids amides, were synthesized and evaluated for antiproliferative activity and cell cycle effects. These synthesized compounds proved to be more hydrophilic, as well as improved or comparable in vitro cytotoxicities against four cell lines (A-549, HeLa, SiHa, and HL-60) compared with either parent DPT or anti-cancer drug VP-16. Furthermore, flow cytometric analysis exhibited that N-(1-oxyl-4'-demethyl-4-deoxypodophyllic)-d-α-methine amide (15f) induced cell cycle arrest in the G2/M phase in A-549 cells.

Regioselective Intermolecular [2 + 2]-Cycloaddition of α-Iodo-Unsaturated Ketones Promoted by Diisobutylaluminum Hydride.

The development of intermolecular [2 + 2]-cycloaddition of α-iodo-unsaturated ketones in the presence of diisobutylaluminum hydride (Dibal-H) is reported to produce various trispirocyclic derivatives containing a cyclobutane ring. This sequential lactonization/[2 + 2]-cycloaddition proceeds in high regioselectivity under mild conditions.