Electrophilic Cyclization of 2-(1-Alkynyl)-2-alken-1-ones Using the I₂/K₃PO₄ System: An Efficient Synthesis of Highly Substituted Iodofurans

The electrophilic cyclization of 2-(1-alkynyl)-2-alken-1-ones in the presence of various alcohols or carbon-based nucleophiles offers an efficient and straightforward route to highly substituted iodofurans under extremely mild reaction conditions. The iodo derivatives are potential synthetic intermediates for amplification of molecular complexity

A Controllable Synthesis of Homoallyl Ketones and Multiply Substituted Cyclopentadienes by Direct Insertion of Aroyl Cyanides to Zirconacyclopentenes

The direct reaction of aroyl cyanides with zirconacyclopentenes was achieved cleanly under controlled reaction conditions. This methodology provided an extremely efficient, one-pot, and high-yield route for the synthesis of homoallyl ketones when the reaction was carried out at −50 °C. Trapping of the zirconium intermediate by a variety of electrophiles afforded functionalized homoallyl ketones. Remarkably, the insertion reaction occurred with complete chemoselectivity, that means, the Zr−sp3 carbon bond reacted preferentially, which is different from Cu-mediated elaboration of zirconacycles. Surprisingly, when the reaction was done at room temperature, 1,2,3-trisubstituted cyclopentadiene derivatives were readily formed in high yields. The direct insertion reaction of zirconacyclopentanes with acyl cyanides was also described. When bicyclic zirconacyclopentanes were used, cyclopentanol derivatives were obtained with high stereoselectivity

A Controllable Synthesis of Homoallyl Ketones and Multiply Substituted Cyclopentadienes by Direct Insertion of Aroyl Cyanides to Zirconacyclopentenes

The direct reaction of aroyl cyanides with zirconacyclopentenes was achieved cleanly under controlled reaction conditions. This methodology provided an extremely efficient, one-pot, and high-yield route for the synthesis of homoallyl ketones when the reaction was carried out at −50 °C. Trapping of the zirconium intermediate by a variety of electrophiles afforded functionalized homoallyl ketones. Remarkably, the insertion reaction occurred with complete chemoselectivity, that means, the Zr−sp3 carbon bond reacted preferentially, which is different from Cu-mediated elaboration of zirconacycles. Surprisingly, when the reaction was done at room temperature, 1,2,3-trisubstituted cyclopentadiene derivatives were readily formed in high yields. The direct insertion reaction of zirconacyclopentanes with acyl cyanides was also described. When bicyclic zirconacyclopentanes were used, cyclopentanol derivatives were obtained with high stereoselectivity

Heterocyclized Carbometalation of Alkynes: Unexpected Formation of Eight-Membered Oxazirconacycles with an Intramolecularly Coordinated Isoquinoline Moiety

The isoquinolyl-zirconation of various unactivated alkynes was investigated by a one-pot, three-component reaction of two different alkynes with a nitrile in the presence of 1 equiv of CuCl. The true nature of the resulting products of novel eight-membered oxazirconacycles containing an intramolecular Zr−N coordination was established using X-ray crystallography

Heterocyclized Carbometalation of Alkynes: Unexpected Formation of Eight-Membered Oxazirconacycles with an Intramolecularly Coordinated Isoquinoline Moiety

The isoquinolyl-zirconation of various unactivated alkynes was investigated by a one-pot, three-component reaction of two different alkynes with a nitrile in the presence of 1 equiv of CuCl. The true nature of the resulting products of novel eight-membered oxazirconacycles containing an intramolecular Zr−N coordination was established using X-ray crystallography

Supplementary document for On-chip photonic convolution by phase-change in-memory computing cells with quasi-continuous tuning - 6826600.pdf

On-chip photonic convolution by phase-change in-memory computing cell with quasi-continuous tuning: supplemental documen

Supplementary document for On-chip photonic convolution by phase-change in-memory computing cells with quasi-continuous tuning - 6912420.pdf

Supplemental Documen

Zinc-Catalyzed Reduction of Amides: Unprecedented Selectivity and Functional Group Tolerance

Zinc-Catalyzed Reduction of Amides: Unprecedented Selectivity and Functional Group Toleranc

General and Selective Copper-Catalyzed Reduction of Tertiary and Secondary Phosphine Oxides: Convenient Synthesis of Phosphines

Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields

Improved Synthesis of Aryl-Substituted Anthracenes and Heteroacenes

A Brønsted acid-catalyzed highly efficient construction of substituted arylanthracenes and heteroacenes is described, which is assumed to be initiated through the facile formation of a benzylic cation intermediate. This method offers several advantages in comparison with known aromatic cyclodehydration reactions such as high selectivities, mild reaction conditions, and easily accessible starting materials