60562-06-3

Upstream product

• 6196-83-4 2-phenyl-2-norbornanol 
• 497-38-1 (1S,4R)-bicyclo[2.2.1]heptan-2-one 
• 100-58-3 phenylmagnesium bromide 
• 108-86-1 bromobenzene 
• 498-66-8 norbornene 
• 591-51-5 phenyllithium 

Relevant academic research and scientific papers

Electro-mediated PhotoRedox Catalysis for Selective C(sp3)–O Cleavages of Phosphinated Alcohols to Carbanions

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3)?O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp3)?O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.

KO:TBu-Catalyzed lithiation of PMDTA and the direct functionalization of bridged alkenes under mild conditions

A practical preparation of the reagent PMDTALi using a super base system under mild conditions has been developed. This PMDTALi base has been demonstrated to be a very efficient reagent for the lithiation of bridged alkenes via direct deprotonation. Further reactions with electrophiles and also coupling reactions in the presence of Pd catalysts provide the bridged alkenes with a broad range of functional groups including silyl, alkyl, halogen and aryl substituents. The utilization of this new lithium reagent has brought a new diversity to the choice of lithium reagent for the deprotonation of synthetically challenging systems.

Carbocation-forming reactions in dimethyl sulfoxide

Mesylate derivatives of 3-aryl-3-hydroxy-β-lactams and thiolactams react in DMSO-d6 by first-order processes to give alcohol products. Substituent effect studies implicate carbocation intermediates (ion-pairs) that are captured by DMSO-d6 to give transient oxosulfonium ions. Rapid reaction of the oxosulfonium ions with trace amounts of water leads to the alcohol product and regenerates DMSO-d6. H217O labeling studies show that 17O is incorporated into the DMSO. The mesylate derivatives of endo- and exo-2-hydroxy-2-phenylbicyclo[2.2.1]heptan-3-one also react in DMSO-d6 to give the alcohol products. Ion-pair intermediates that capture DMSO giving unstable oxosulfonium ions are again proposed. Exo-2-phenyl-endo-bicyclo[2.2.1]heptyl trifluoroacetate readily eliminates trifluoroacetic acid in DMSO-d6 via a cationic mechanism involving loss of the endotrifluoroacetate leaving group as well as an exo-hydrogen. The O-methyl oxime derivative of α-chloroα,α-diphenylacetophenone reacts in DMSO-d6 to give 1-methoxy-2,3-diphenylindole, a product derived from cyclization of a cationic intermediate. A common ion rate suppression provides further evidence for a cationic mechanism. The triflate derivative of pivaloin reacts by a cationic mechanism in DMSO-d6 to give rearranged products. The rate is even faster than in highly ionizing solvents such as trifluoroethanol or trifluoroacetic acid. 1-Adamantyl mesylate reacts in DMSO-d6 by a first-order process (YOMs = -4.00) to give a long-lived oxosulfonium ion, 1-Ad-OS(CD3)2+, which can be characterized spectroscopically. This oxosulfonium ion reacts only slowly with water at elevated temperatures to give 1-adamantanol. DMSO is therefore a viable solvent for ks, kC, and kΔ cationic processes.

The Relaxed and Spectroscopic Energies of Olefin Triplets

The relaxed energies and lifetimes of a series of olefin triplets have been determined by time-resolved photoacoustic calorimetry using a novel cell configuration which allows improved precision.The planar triplet energies of a number of olefins were meas