Kanako Nozawa‐Kumada

The synthesis of isoindolinones via copper-catalyzed sp(3) C-H functionalization of 2-alkyl-N-substituted benzamides is described. This process does not require the preparation of halogenated substitutes, expensive transition metals, or toxic Sn or CO gas. This method provides an efficient approach to generate various functionalized isoindolinones.

Herein, we describe the first oxysilylation of unsaturated carboxylic acids mediated by di-<i>tert</i>-butyl peroxide (DTBP), which enables the rapid and efficient preparation of silyl lactone compounds. This process tolerates functional groups, such as methyl, methoxy, halogen (fluoride and chloride), and cyano moieties. Furthermore, the strategy allows the application of a wide range of primary, secondary, and tertiary hydrosilanes for functionalization.

Herein, we report an efficient and practical hydroiodination of internal alkynes using HI generated <i>ex situ</i> from the readily available triethylsilane and I₂. This system offers high regio- and stereoselectivity to afford (<i>E</i>)-vinyl iodides in good yields under mild conditions. Furthermore, the hydroiodination reaction shows high functional group tolerance toward alkyl, methoxy, halogen, trifluoromethyl, cyano, ester, halomethyl, acid-sensitive silyl ether, and acetal moie

A method for the deprotonative silylation of aromatic C-H bonds has been developed using trifluoromethyltrimethylsilane (CF₃SiMe₃, Ruppert-Prakash reagent) and a catalytic amount of fluoride. In this reaction, CF₃SiMe₃ is considered to act as a base and a silicon electrophile. This process is highly tolerant to various functional groups on heteroarenes and benzenes. Furthermore, this method can be applied to the synthesis of trimethylsilyl group-contai

β-Lactams are important structural motifs because of their ubiquity in natural products and pharmaceuticals. We report herein a Cu-catalyzed intramolecular oxidative C(sp³ )-H amidation for the synthesis of β-lactams using tBuOOtBu. This method is based on Kharasch-Sosnovsky amidation and does not require prefunctionalization of C(sp³ )-H bonds or the installation of a directing group, thereby allowing for the straightforward synthesis of β-lactams. Our intramolecular funct

Abstract An inexpensive, powerful, and eco‐friendly method for transition‐metal‐free oxidative C(sp 3 )−H bond lactonization was developed using sodium peroxydisulfate as the sole oxidant. The cyclization of 2‐alkylbenzoic acids containing a primary, secondary or tertiary carbon at the benzylic position proceeded smoothly, affording a variety of lactone derivatives. Furthermore, various functional groups such as halogen, cyano, nitro and hydroxy groups were tolerated under the reaction condition

The transformation of nitrobenzenes into azobenzenes by pyridine-derived super electron donor 2 is described. This method provides an efficient synthesis of azobenzenes because of not requiring the use of expensive transition-metals, toxic or flammable reagents, or harsh conditions. Moreover, when using 2-fluoronitrobenzenes as substrates, phenazines were found to be obtained. The process affords a novel synthesis of phenazines.

Abstract A chemoselective silylation of terminal alkynes with trifluoromethyltrialkylsilane in 1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1 H )‐pyrimidinone (DMPU) is described. This process is effective even under mild conditions without the use of fluorides or an N‐heterocyclic carbene (NHC), providing a widely applicable method for the synthesis of alkynylsilicon compounds. Moreover, it was found that the preferential deprotonation of terminal alkynes using this system proceeded faster than the triflu

A copper-catalyzed aerobic 3-hydroxyisoindolinone synthesis was developed via the benzylic double C(sp³)-H functionalization of 2-alkylbenzamides. In this reaction, molecular oxygen was used as both an oxidant for C(sp³)-H functionalization and an oxygen source. Our method can be extended to diverse benzylic C(sp³)-H bonds and shows excellent functional group tolerance.

The desulfurization of thioacetals and thioethers by a pyridine-derived electron donor is described. This methodology provides efficient access to the reduced products in high yields and does not require the use of transition-metals, elemental alkali-metals, or hydrogen atom donors.

Transition-metal-free coupling of haloarenes with unactivated arenes has been developed in the presence of NaH and 1,10-phenanthroline. Various haloarenes bearing methyl, methoxy, halogen (fluoride, chloride, and bromide), cyano, trifluoromethyl, ester, and amide groups can be cross-coupled with unactivated arenes, or heteroarenes in this reaction.

Abstract An S N 2‐type trifluoromethylation of benzyl halides under transition‐metal‐free conditions has been developed using trifluoromethyltrimethylsilane (CF 3 SiMe 3 , Ruppert−Prakash reagent) and CsF in 1,2‐dimethoxyethane (DME). Under the developed reaction conditions, the in situ generated trifluoromethyl anion (CF 3 − ) overcame the instability and displayed enhanced nucleophilicity in the presence of DME. This method provides an efficient approach for the generation of various (2,2,2‐tr

A transition-metal-free intermolecular coupling reaction of halocompounds with styrenes in the presence of NaH and 1,10-phenanthroline was developed. This reaction afforded hydrocarbonated products with complete anti-Markovnikov selectivity. The method allows the use of a wide range of halocompounds, including aryl and alkyl halides, and good functional group tolerance. Detailed mechanistic studies indicated that an anilide anion generated in situ by the NaH-mediated reduction of 1,10-phenanthro

Abstract Herein, we report a copper‐catalyzed intramolecular benzylic C( sp 3 )−H oxidation of unprotected aniline derivatives under aerobic conditions, which enables the preparation of phenanthridine compounds. To the best of our knowledge, this is the pioneering reaction of dehydrogenative C( sp 3 )−N bond formation from unprotected anilines under a Cu/O 2 system. Notably, various anilines possessing alkyl, methoxy, halogen (fluoride, chloride, bromide, and iodide), trifluoromethyl, trifluorom

Biaryls are important compounds with widespread applications in many fields. Tetramethylammonium fluoride tetrahydrate was found to promote the biaryl coupling of aryl iodides bearing electron-withdrawing substituents with unactivated arenes. The reaction takes place at temperatures between 100 and 150°C and can be applied to a wide range of aromatic and heteroaromatic rings, affording the products in moderate to high yields. The reaction does not require strong bases or expensive additives that