16704-45-3

Upstream product

• 95-78-3 2,5-Dimethylaniline 
• 108-98-5 thiophenol 
• 132907-18-7 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene 
• 106-42-3 para-xylene 
• 14204-27-4 N-phenylthiophthalimide 
• 553-94-6 4-bromo-m-xylene 
• 4670-62-6 tetra-N-butylammonium benzenethiolate 
• 4001-61-0 2,5-dimethylthiophenol 
• 98-80-6 phenylboronic acid 
• 1193-82-4 racemic methyl phenyl sulfoxide 

Downstream Products

• 16704-49-7 Phenyl-2,5-dimethyl-phenyl-sulfoxid 

Relevant academic research and scientific papers

Metal-free C-H thioarylation of arenes using sulfoxides: A direct, general diaryl sulfide synthesis

Metal-free C-H thioarylation of arenes and heteroarenes using methyl sulfoxides constitutes a general protocol for the synthesis of high value diaryl sulfides. The coupling of arenes and heteroarenes with in situ activated sulfoxides is regioselective, uses readily available starting materials, is operationally simple, and tolerates a wide range of functional groups.

Silver catalyzed C-C and C-S coupling of aryl halides and thiols with boronic acids

An efficient Ag(I) catalyzed carbon-carbon and carbon-sulfur bond formation reaction of aryl halides and thiols with boronic acids has been demonstrated. Using this protocol, substrates with a wide range of functional group including electron-rich, and electron deficient substituents have been explored. These reactions are particularly useful to prepare symmetrical and unsymmetrical biphenyls and thioethers. These products were isolated in high yield.

Iodonium Cyclophanes for SECURE Arene Functionalization

This disclosure relates to compounds, reagents, and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. For example, this disclosure provides universal “locked” aryl substituents that result in StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) from diaryliodonium salts. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.

Regiospecific reductive elimination from diaryliodonium salts

(Figure Presented) Out-of-plane steric bulk furnished by a cyclophane substituent on iodine(III) strongly destabilizes the transition state in the reductive elimination from diaryliodonium salts and leads to regiochemical control (dubbed SECURE), as is demonstrated by computational and experimental studies. This approach should be general for high-valent maingroup and transition metal ions. X=N3, OAc, PhO, CF3CH2O, SCN, PhS.

AlCl3-mediated aromatic phenylthiation with N-phenylthiophthalimide

N-Phenylthiophthalimide reacts with AlCl3 or TiCl4 in arenes to give phenylthiated arenes alone via a phenylsulfenium ion intermediate, modified neglect of diatomic overlap (MNDO) molecular orbital calculations of which revealed that the positive charge preferentially populates the sulfur atom rather than the phenyl group in the phenylsulfenium ion.

REACTIVITY OF 3,6-DIMETHOXY-3,6-DIMETHYLCYCLOHEXA-1,4-DIENE: NUCLEAR VERSUS BENZYLIC NUCLEOPHILIC SUBSTITUTION

The treatment of cis/trans-3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (ca. 1/1 mixture; easily prepared electrochemically in multigram scale from p-xylene) under acidic conditions (acetic, trifluoroacetic, sulfuric, or a Lewis acid) yields almost exclusively 2-methoxy-1,4-dimethylbenzene 4, through a trasposition reaction.The use of aqueous hydrochloric or hydrofluoric acid gives 2,5-dimethylphenol 12, and with hydrogen chloride a mixture of 2- and α-chloro-p-xylene (13, 14) is isolated.Different oxygen-, nitrogen-, and sulfur-containing nucleophiles (alcohols,thiols, or hydrazoic acid) react with 3 under acid catalysis giving the corresponding products resulting from a nuclear or/ and benzylic substitution on p-xylene (15 - 20).The reaction of compound 3 with organolithium reagents affords exclusively benzylic products 21 in a regiospecific manner.In all cases the mixtures of isomers are separated by column chromatography.The lithiation of compound 3 with lithium powder or lithium naphthalenide fails, giving p-xylene.A probable mechanism is proposed for the studied reactions.