37608-93-8

Upstream product

• 54288-06-1 4,4-dimethyl-1-phenyl-1-pentanol 
• 2855-08-5 1-chloro-3,3-dimethylbutane 
• 100-47-0 benzonitrile 
• 1647-23-0 3,3-dimethylbutyl bromide 
• 557-20-0 diethylzinc 
• 29569-93-5 (E)-4,4-dimethyl-1-phenylpent-2-en-1-one 
• 66688-49-1 1-iodo-2-iodomethyl-2-methylpropane 
• 98-86-2 acetophenone 
• 15501-33-4 neopentyl iodide 
• 558-37-2 tert-butylethylene 
• 100-52-7 benzaldehyde 
• 100-51-6 benzyl alcohol 
• 27845-50-7 (E)-N-benzylidenebenzylamine 
• 100-46-9 benzylamine 

Downstream Products

• 138432-96-9 4,4-dimethyl-2-phenyl-2-hexanol 

Relevant academic research and scientific papers

Rhodium-Catalyzed Regioselective and Chemoselective Deoxygenative Reduction of 1,3-Diketones

The deoxygenative reduction of carbonyl compounds has been well established. However, most protocols developed typically require harsh reaction conditions or highly reactive/toxic reagents, and the deoxygenative reduction of 1,3-diketones is rarely explored despite their importance to synthetic chemistry and materials science. We describe here a rhodium-catalyzed regioselective and chemoselective deoxygenative reduction of 1,3-diketones under mild reaction conditions. This approach exhibited exceptionally high regioselectivity toward the aliphatic carbonyl reduction over aromatic carbonyl reduction. Moreover, the reaction showed good functional group tolerance and broad substrate scope as well as great potential in the late-stage modification and synthesis of natural products and pharmaceutical skeletons. Preliminary mechanistic studies and DFT calculations revealed that this reaction involved the deoxygenation of 1,3-diketone to α, β-unsaturated ketone and its subsequent 1,4-reduction. The noticeably lower energy barrier of the aliphatic C═O insertion into [Rh]-Bpin versus the aromatic C═O insertion was responsible for the high regioselectivity in this reduction.

KOtBu/DMSO Catalytic System for Isomerization of Allylic Alcohols to Ketones

The isomerization of allylic alcohols is an important reaction because it can afford carbonyl compounds in an atom-economical manner. Although base-catalyzed methods are more desirable than those using transition-metal catalysts from both the economic and environmental points of view, these methods have several drawbacks, such as narrow substrate scope and high catalyst loading. This paper reports the development of an efficient KOtBu/DMSO catalytic system suitable for the isomerization of a broad range of allylic alcohols with good yields, to which previously reported systems could not be applied. This catalytic system was successfully applied to a tandem allylic isomerization/electrophilic trapping reaction, thereby highlighting its synthetic utility.

Diels-Alder route to norbornane derived vicinal phosphane/borane frustrated Lewis pairs for the metal-free catalytic hydrogenation of α, β-unsaturated ketones

The [4+2] cycloaddition reaction of the (dimesitylphosphino)cyclopentadienes 5a,b with N-phenylmaleimide gave the norbornene derivative 9. Its reduction with LiAlH4 produced the N-phenylpyrrolidino-annulated system 10. Treatment with Piers' bor

Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates

Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.

Solvent-free direct α-alkylation of ketones by alcohols catalyzed by nickel supported on silica-alumina

The α-alkylation of acetophenone with benzyl alcohol through borrowing hydrogen has been studied using nickel catalysis. Ni/SiO2-Al2O3 was found to be the best catalyst for this transformation and the corresponding alkylated acetophenone was obtained with 93% isolated yield. Following the objectives of clean and sustainable chemistry, the reaction occurs under solvent-free conditions and requires only a catalytic amount of base. This protocol was next applied to a wide range of ketones and alcohols and the desired products were isolated with 18-86% yields (26 examples). The recovery and recyclability of the nickel catalyst was also investigated and it was found to be active over 5 runs without significant loss of activity. Surprisingly, the active catalyst appears to include an amorphous nickel hydroxide layer.

Direct β-Alkylation of Ketones and Aldehydes via Pd-Catalyzed Redox Cascade

We report a direct β-alkylation of ketones and aldehydes with simple alkyl bromides through a Pd-catalyzed redox-cascade strategy. The use of a Cu cocatalyst is important for improved efficiency. The reaction is redox-neutral, without the need for strong acids or bases. Both cyclic and acyclic ketones, as well as α-branched aldehydes, are suitable substrates for coupling with secondary and tertiary alkyl bromides. Concise formal synthesis of Zanapezil is achieved using this β-alkylation method.

Direct Decarboxylative-Decarbonylative Alkylation of α-Oxo Acids with Electrophilic Olefins via Visible-Light Photoredox Catalysis

The decarbonylation of primary, secondary, and tertiary alkyl-substituted acyl radicals has been investigated through photoredox catalysis. A series of quaternary carbons and γ-ketoesters have been directly constructed by the photoredox 1,4-conjugate addi

Iron-Catalyzed Radical Decarboxylative Oxyalkylation of Terminal Alkynes with Alkyl Peroxides

An iron-catalyzed oxyalkylation of alkynes with alkyl peroxides as the alkylating reagents has been investigated. Alkyl peroxides are readily available from aliphatic acids and serve simultaneously as the alkylating reagents and internal oxidants. Primary, secondary, and tertiary alkyl groups of aliphatic acids were readily incorporated into C?C triple bonds and diverse α-alkylated ketones were synthesized. Mechanism studies revealed that this reaction involves highly reactive alkyl free radicals. A unique equilibrium between lauric acid and water catalyzed by the iron(III) catalyst was observed.

Traceless chelation-controlled rhodium-catalyzed intermolecular alkene and alkyne hydroacylation

A new functional-group tolerant, rhodium-catalyzed, sulfide-reduction process is combined with rhodium-catalyzed chelation-controlled hydroacylation reactions to give a traceless hydroacylation protocol. Aryl- and alkenyl aldehydes can be combined with both alkenes, alkynes and allenes to give traceless products in high yields. A preliminary mechanistic proposal is also presented. Traceless catalysis: The powerful combination of a chelation-controlled hydroacylation process and a new rhodium-catalyzed sulfide reduction gave the products of traceless hydroacylation. Aryl- and alkenyl aldehydes can be combined with alkenes, alkynes, and allenes to deliver traceless products in high yields (see scheme). Copyright

Double hydroacylation reactions of acyclic and cyclic α,β- unsaturated aldehydes

Double or quits? double hydroacylation reactions of acyclic and cyclic α,β-unsaturated aldehydes with olefins afford ketone and diketone products, respectively. Enantiomers are formed whose absolute configurations are controlled by the order of alkene addition.