Amberlyst-A26-Mediated Corey-Chaykovsky Cyclopropanation of 9-Alkylidene-9H-fluorene under Continuous Process.

Herein, we have developed a continuous-process for the direct cyclopropanation of various alkenes nonconjugated with carbonyl using trimethylsulfoxonium iodide as a methylene source via the Corey-Chaykovsky cyclopropanation reaction in the presence of Amberlyst-A26 as a heterogeneous base. Several 9-alkylidene-9H-fluorene derivatives successfully undergo Corey-Chaykovsky cyclopropanation to afford spiro[cyclopropane-1,9'-fluorene] in excellent yields under the continuous-process module. Furthermore, continuous process for the cyclopropanation of 3-benzylideneindolin-2-one derivatives using Amberlyst-A26 as a heterogeneous base has been described, which afford spiro[cyclopropane-1,3'-indolin]-2'-one derivatives.

Transition-Metal-Free Alkylative Aromatization of Tetralone Using Alcohol/Amino Alcohol towards the Synthesis of Bioactive Naphthol and Benzo[e/g]indole Derivatives.

Herein, we report alkylative aromatization of tetralone for the synthesis of bioactive naphthols and benzo[e/g]indole derivatives using alcohols in the presence of NaOH via an aerobic oxidative cross-coupling protocol. This is a general and transition-metal-free method, which uses an inexpensive base, avoids inert conditions, and furnishes water and hydrogen peroxide as the byproducts. Moreover, this method demonstrated with wide substrate scope and obtained exclusive regioselectivity.

Lewis Acid-Catalyzed Chemodivergent and Regiospecific Reaction of Phenols with Quaternary Peroxyoxindoles.

The indium-catalyzed regiospecific coupling of substituted phenol derivatives and quaternary peroxyoxindoles for the synthesis of C2 or C4 benzoxazin-3-one-substituted phenols via skeletal rearrangement is described. This reaction is demonstrated with 17 examples with good yields and diverse aryl substituents. In contrast to the indium-catalyzed reaction, the Cu(OTf)2-catalyzed reaction of the phenol with quaternary peroxyoxindoles afforded C2 or C4 2-oxindole-substituted phenol derivatives. This diverse catalytic reaction generated various biologically important phenol-substituted 2-oxindole derivatives directly without any skeleton rearrangement and was demonstrated with 19 examples in high yield. The regiospecificity and the reaction pathways were explained with the support of density functional theory (DFT).

Sequential Oxidative Fragmentation and Skeletal Rearrangement of Peroxides for the Synthesis of Quinazolinone Derivatives.

For the first time, the sequential reaction of peroxyoxindole that involves base-promoted oxidative fragmentation to isocyanate formation and primary amine or amino alcohol accelerated skeletal rearrangement to synthesize exo-olefinic-substituted quinazolinone or oxazoloquinazolinone is reported. The advantages of this new reaction include a broad substrate scope and transition-metal-free and room-temperature conditions. The formation of the isocyanate as a key intermediate that accelerates oxidative skeletal rearrangement has been confirmed by trapping experiments and spectroscopic evidence.

Manganese-Catalyzed Synthesis of Quaternary Peroxides: Application in Catalytic Deperoxidation and Rearrangement Reactions.

Highly efficient, selective, and direct C-H peroxidation of 9-substituted fluorenes has been achieved using a Mn-2,2'-bipyridine catalyst via radical-radical cross-coupling. Moreover, this method effectively promotes the vicinal bisperoxidation of sterically hindered various substituted arylidene-9H-fluorene/arylideneindolin-2-one derivatives to afford highly substituted bisperoxides with high selectivity over the oxidative cleavage of C═C bond that usually forms the ketone of an aldehyde. Furthermore, a new approach for the synthesis of (Z)-6-benzylidene-6H-benzo[c]chromene has been achieved via an acid-catalyzed skeletal rearrangement of these peroxides. For the first time, unlike O-O bond cleavage, reductive C-O bond cleavage in peroxides using the Pd catalyst and H2 is described, which enables the reversible reaction to afford exclusively deperoxidized products. A detailed mechanism for peroxidation, molecular rearrangement, and deperoxidation has been proposed with preliminary experimental evidences.

Ligand-Free Ru-Catalyzed Direct sp3 C-H Alkylation of Fluorene Using Alcohols.

The sp3 C-H alkylation of 9H-fluorene using alcohol and a Ru catalyst via the borrowing hydrogen concept has been described. This reaction was catalyzed by the [Ru(p-cymene)Cl2]2 complex (3 mol %) and exhibited a broad reaction scope with different alcohols, allowing primary and secondary alcohols to be employed as nonhazardous and greener alkylating agents with the formation of environmentally benign water as a byproduct. A variety of 9H-fluorene underwent selective and exclusive mono-C9-alkylation with primary alcohols in good to excellent isolated yield (26 examples, 50-92% yield), whereas this reaction with secondary alcohols in the absence of any external oxidants furnished the tetrasubstituted alkene as the major product. Furthermore, a base-mediated C-H hydroxylation of the synthesized 9H-fluorene derivatives afforded 9H-hydroxy-functionalized quaternary fluorene derivatives in excellent yield.