154318-75-9

Upstream product

• 98-54-4 para-tert-butylphenol 
• 421-83-0 trifluoromethane sulfonyl chloride 
• 2926-30-9 sodium triflate 
• 123324-71-0 p-tert-butylphenylboronic acid 
• 132993-22-7 2-nitrophenyl trifluoromethanesulfonate 
• 17763-80-3 para-nitrophenyl triflate 
• 358-23-6 trifluoromethylsulfonic anhydride 

Downstream Products

• 939-97-9 4-tert-Butylbenzaldehyde 
• 1625-91-8 4,4'-di-tert-butylbiphenyl 
• 255835-92-8 (4-tert-butylphenyl)(4-methoxyphenyl)amine 
• 1625-92-9 4-tert-butylbiphenyl 
• 1005759-24-9 5-(4-tert-butylphenyl)thiophene-2-carbonitrile 
• 1005759-21-6 5-(4-tert-butylphenyl)-2-n-propylthiazole 
• 4496-49-5 4-tert-butyldiphenylamine 
• 7364-19-4 4-ethyl-tert-butylbenzene 
• 1216934-33-6 1-(1-butoxyvinyl)-4-tert-butyl benzene 
• 64-18-6 formic acid 
• 253185-03-4 tert-butylbenzene 
• 109-87-5 Dimethoxymethane 
• 616-42-2 dimethylsulfite 
• 75-46-7 trifluoromethan 

Relevant academic research and scientific papers

Practical Synthesis of Aryl Triflates under Aqueous Conditions

A practical and efficient synthesis of aryl triflates under biphasic basic aqueous conditions is described. The current methodology provides entry into these valuable substrates that omits the use of amine bases and allows facile isolation by s

Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis

Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report a dynamic kinetic cross-coupling approach for the direct functionalization of alcohols. The feasibility of this strategy is demonstrated by a nickel-catalyzed cross-electrophile arylation reaction of benzyl alcohols with (hetero)aryl electrophiles. The reaction proceeds with a broad substrate scope of both coupling partners. The electron-rich, electron-poor, and ortho-/meta-/para-substituted (hetero)aryl electrophiles (e.g., Ar-OTf, Ar-I, Ar-Br, and inert Ar-Cl) all coupled well. Most of the functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar-SiMe3, Ar-Bpin, and Ar-SnBu3, were tolerated. The dynamic nature of this method enables the direct arylation of benzylic alcohol in the presence of various nucleophilic groups, including nonactivated primary/secondary/tertiary alcohols, phenols, and free indoles. It thus offers a robust alternative to existing methods for the precise construction of diarylmethanes. The synthetic utility of the method was demonstrated by a concise synthesis of biologically active molecules and by its application to peptide modification and conjugation. Preliminary mechanistic studies revealed that the reaction of in situ formed benzyl oxalates with nickel, possibly via a radical process, is an initial step in the reaction with aryl electrophiles.

Palladium-Catalyzed Synthesis of N, N-Dimethylanilines via Buchwald-Hartwig Amination of (Hetero)aryl Triflates

This work delineates the synthesis of N,N-dimethylaniline derivatives from dimethylamines and aryl triflates. The palladium-catalyzed C-N bond formation proceeds in excellent yields, using an unsophisticated catalytic system, a mild base, and triflates as electrophiles, which are readily available from inexpensive phenols. N,N-Dimethylanilines are multifunctional reaction partners and represent useful but underutilized building blocks in organic synthesis.

Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds

Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.

Palladium-Catalyzed Cyclobutanation of Aryl Sulfonates through both C-O and C-H Cleavage

A palladium-catalyzed cyclobutanation of aryl sulfonates with strained alkenes has been developed. The methodology is featured to achieve the cleavage of both C-O and C-H bonds of phenol derivatives in one pot. Under the reaction conditions, in addition t

Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts

Herein we present a Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle. An electron-deficient sulfone ligand proved to be key for the successful implementation of this protocol, which allows the unusual construction of C(sp2)-O bonds using commercially available NaOTf and KONf as coupling partners. Preliminary mechanistic studies as well as theoretical investigations reveal the intermediacy of a highly electrophilic Bi(V) species, which rapidly eliminates phenyl triflate.

Reductive Coupling between C-N and C-O Electrophiles

The cross-electrophile reaction is a promising strategy for C-C bond formation. Recent studies have focused mainly on reactions with organic halides. Here we report a coupling reaction between C-N and C-O electrophiles that demonstrates the possibility of constructing a C-C bond via C-N and C-O cleavage. Several reactions between benzyl/aryl ammonium salts and vinyl/aryl C-O electrophiles have been studied. Preliminary mechanistic studies revealed that the benzyl ammoniums were activated through a radical mechanism.

Transition-Metal-Free C-C, C-O, and C-N Cross-Couplings Enabled by Light

Transition-metal-catalyzed cross-couplings to construct C-C, C-O, and C-N bonds have revolutionized chemical science. Despite great achievements, these metal catalysts also raise certain issues including their high cost, requirement of specialized ligands, sensitivity to air and moisture, and so-called "transition-metal-residue issue". Complementary strategy, which does not rely on the well-established oxidative addition, transmetalation, and reductive elimination mechanistic paradigm, would potentially eliminate all of these metal-related issues. Herein, we show that aryl triflates can be coupled with potassium aryl trifluoroborates, aliphatic alcohols, and nitriles without the assistance of metal catalysts empowered by photoenergy. Control experiments reveal that among all common aryl electrophiles only aryl triflates are competent in these couplings whereas aryl iodides and bromides cannot serve as the coupling partners. DFT calculation reveals that once converted to the aryl radical cation, aryl triflate would be more favorable to ipso substitution. Fluorescence spectroscopy and cyclic voltammetry investigations suggest that the interaction between excited acetone and aryl triflate is essential to these couplings. The results in this report are anticipated to provide new opportunities to perform cross-couplings.

Enantioselective Synthesis of α-Allyl Amino Esters via Hydrogen-Bond-Donor Catalysis

We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of α-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via nucleophilic allylation of readily accessible α-chloro glycinates. A variety of useful α-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% ee) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the α-chloro glycinate and the nucleophile, consistent with rate-limiting C-C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted SN2 mechanism.

A simple route to 1,4-addition reactions by Co-catalyzed reductive coupling of organic tosylates and triflates with activated alkenes

An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.