13328-80-8

Upstream product

• 34818-50-3 isochroman-1-yl acetate 
• 7677-24-9 trimethylsilyl cyanide 
• 34818-49-0 1-methoxyisochromane 
• 131869-38-0 1-(t-butylperoxy)-3,4-dihydro-1H-isochromene 
• 95033-78-6 1-hydroxyisochroman 
• 493-05-0 isochromane 
• 19158-51-1 P-toluenesulfonyl cyanide 
• 172876-96-9 3-oxo-1λ³-benzo[d][1,2]iodaoxole-1(3H)-carbonitrile 
• 60-12-8 2-phenylethanol 
• 31253-52-8 α-chloroisochroman 

Relevant academic research and scientific papers

C(sp3)?H Cyanation Promoted by Visible-Light Photoredox/Phosphate Hybrid Catalysis

Inspired by the reaction mechanism of photo-induced DNA cleavage in nature, a C(sp3)?H cyanation reaction promoted by visible-light photoredox/phosphate hybrid catalysis was developed. Phosphate radicals, generated by one-electron photooxidation of phosphate salt, functioned as a hydrogen-atom-transfer catalyst to produce nucleophilic carbon radicals from C(sp3)?H bonds with a high bond-dissociation energy. The resulting carbon radicals were trapped by a cyano radical source (TsCN) to produce the C?H cyanation products. Due to the high functional-group tolerance and versatility of the cyano group, the reaction will be useful for realizing streamlined building block syntheses and late-stage functionalization of drug-like molecules.

A metal-free direct C (sp3)-H cyanation reaction with cyanobenziodoxolones

A metal-free protocol of direct C(sp3)-H cyanation with cyanobenziodoxolones functioning as both cyanating reagents and oxidants was developed. Unactivated substrates, such as alkanes, ethers and tertiary amines, were thereby transformed to the corresponding nitriles in moderate to high yields. Mechanistic studies indicated that the cyanation proceeded with two potential pathways, which is highly dependent on the substrates: (1) a free radical case for alkanes and ethers and (2) an oxidative case for tertiary amines.

Merging Photoredox with Br?nsted Acid Catalysis: The Cross-Dehydrogenative C?O Coupling for sp3 C?H Bond Peroxidation

A photoredox and Br?nsted acid synergistically catalyzed cross-dehydrogenative C?O coupling reaction is developed in which isochroman peroxyacetals are formed through sp3 C?H bond peroxidation. The reported method is characterized by its extremely mild reaction conditions, excellent yields, and broad substrate scope. An oxocarbenium ion p-chlorobenzenesulfonate was speculated to be the reactive intermediate. The role of hemiacetals and oxygenated dimers on the effective stabilization of the oxocarbenium ion was investigated; the presence of acid appeared to establish equilibrium between hemiacetals and oxygenated dimers with the oxocarbenium ion pairs. The broad applicability of the method highlights the potential of the protocol for molecule synthesis.

DDQ-mediated Direct C(sp3)-H Cyanation of Benzyl Ethers and 1,3-Diarylpropenes under Solvent- and Metal-free Conditions

A direct cyanation of benzyl ethers and 1,3-diarylpropenes with TMSCN was performed under solvent- and metal-free conditions. This oxidative cross dehydrative coupling (CDC) reaction was promoted by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and provided rapid access to a broad range of nitriles in good to excellent yields.

TRIMETHYLSILYL CYANIDE PROMOTED CYANATION OF TERTIARY ALKYL CHLORIDES AND OTHER SN1 ACTIVE COMPOUNDS

Tertiary chlorides are readily cyanated in a one-pot procedure using trimethylsilyl cyanide in the presence of SnCl4.The mechanism of this novel and synthetically useful reaction involves initial isonitrile formation followed by rearrangement to the tertiary nitrile.Other SN1 active compounds also undergo smooth cyanation.