51171-72-3

Usage

Synthesis Reference(s)

Tetrahedron, 51, p. 12955, 1995 DOI: 10.1016/0040-4020(95)00817-R

Upstream product

• 106993-93-5 2-phenyl-5-oxo-hexanal 
• 637-88-7 1,4-Cyclohexanedione 
• 4894-75-1 1-phenyl-4-cyclohexanone 
• 201230-82-2 carbon monoxide 
• 56671-82-0 3-Iodocyclohex-2-enone 
• 591-51-5 phenyllithium 
• 57044-58-3 (E)/(Z)-β-Trimethylsiloxystyrene 
• 122-78-1 phenylacetaldehyde 
• 78-94-4 methyl vinyl ketone 
• 5769-13-1 4-phenyl-cyclohexanol 
• 15232-96-9 3-phenyl-1-cyclohexene 
• 4096-34-8 cyclohex-3-enone 
• 98-80-6 phenylboronic acid 
• 106993-92-4 dimethoxy-1,1 phenyl-2 hexanone-5 

Downstream Products

• 6312-13-6 3-methyl-4-phenylcyclohex-2-en-1-one 
• 180005-00-9 3-methyl-4-phenylcyclohexanone 
• 1133717-15-3 (S)-4-phenylcyclohexenone 
• 1133717-01-7 C₁₃H₁₃NO₃ 
• 1410070-70-0 N-(2-chloro-4-methylphenyl)-3-iodobiphenyl-4-amine 
• 1410070-96-0 N-(2-chloro-4-methylphenyl)biphenyl-4-amine 
• 1410070-72-2 N-(2,4-dichlorophenyl)-3-iodobiphenyl-4-amine 
• 1410071-06-5 N-(2,4-dichlorophenyl)biphenyl-4-amine 
• 1449248-86-5 2-iodo-4-phenylcyclohex-2-en-1-one 
• 92-69-3 4-Phenylphenol 
• 147678-90-8 N-(4-(methyl)phenyl)-[1,1′-biphenyl]-4-amine 

Relevant academic research and scientific papers

Platinum-Catalyzed α,β-Desaturation of Cyclic Ketones through Direct Metal–Enolate Formation

The development of a platinum-catalyzed desaturation of cyclic ketones to their conjugated α,β-unsaturated counterparts is reported in this full article. A unique diene-platinum complex was identified to be an efficient catalyst, which enables direct metal-enolate formation. The reaction operates under mild conditions without using strong bases or acids. Good to excellent yields can be achieved for diverse and complex scaffolds. A wide range of functional groups, including those sensitive to acids, bases/nucleophiles, or palladium species, are tolerated, which represents a distinct feature from other known desaturation methods. Mechanistically, this platinum catalysis exhibits a fast and reversible α-deprotonation followed by a rate-determining β-hydrogen elimination process, which is different from the prior Pd-catalyzed desaturation method. Promising preliminary enantioselective desaturation using a chiral-diene-platinum complex has also been obtained.

Bidentate Nitrogen-Ligated I(V) Reagents, Bi(N)-HVIs: Preparation, Stability, Structure, and Reactivity

Hypervalent iodine(V) reagents are a powerful class of organic oxidants. While the use of I(V) compounds Dess-Martin periodinane and IBX is widespread, this reagent class has long been plagued by issues of solubility and stability. Extensive effort has been made for derivatizing these scaffolds to modulate reactivity and physical properties but considerable room for innovation still exists. Herein, we describe the preparation, thermal stability, optimized geometries, and synthetic utility of an emerging class of I(V) reagents, Bi(N)-HVIs, possessing datively bound bidentate nitrogen ligands on the iodine center. Bi(N)-HVIs display favorable safety profiles, improved solubility, and comparable to superior oxidative reactivity relative to common I(V) reagents. The highly modular synthesis and in situ generation of Bi(N)-HVIs provides a novel and convenient screening platform for I(V) reagent and reaction development.

Electrochemically driven desaturation of carbonyl compounds

Electrochemical techniques have long been heralded for their innate sustainability as efficient methods to achieve redox reactions. Carbonyl desaturation, as a fundamental organic oxidation, is an oft-employed transformation to unlock adjacent reactivity through the formal removal of two hydrogen atoms. To date, the most reliable methods to achieve this seemingly trivial reaction rely on transition metals (Pd or Cu) or stoichiometric reagents based on I, Br, Se or S. Here we report an operationally simple pathway to access such structures from enol silanes and phosphates using electrons as the primary reagent. This electrochemically driven desaturation exhibits a broad scope across an array of carbonyl derivatives, is easily scalable (1–100 g) and can be predictably implemented into synthetic pathways using experimentally or computationally derived NMR shifts. Systematic comparisons to state-of-the-art techniques reveal that this method can uniquely desaturate a wide array of carbonyl groups. Mechanistic interrogation suggests a radical-based reaction pathway. [Figure not available: see fulltext.]

CeO2-Supported Pd(II)-on-Au Nanoparticle Catalyst for Aerobic Selective α,β-Desaturation of Carbonyl Compounds Applicable to Cyclohexanones

Direct selective desaturation of carbonyl compounds to synthesize α,β-unsaturated carbonyl compounds represents an environmentally benign alternative to classical stepwise procedures. In this study, we designed an ideal CeO2-supported Pd(II)-on-Au nanoparticle catalyst (Pd/Au/CeO2) and successfully achieved heterogeneously catalyzed selective desaturation of cyclohexanones to cyclohexenones using O2 in air as the oxidant. Besides cyclohexenones, various bioactive enones can also be synthesized from the corresponding saturated ketones under open air conditions in the presence of Pd/Au/CeO2. Preliminary mechanistic studies revealed that α-C-H bond cleavage in the substrates is the turnover-limiting step of this desaturation reaction.

Enantioselective Synthesis of γ-Functionalized Cyclopentenones and δ-Functionalized Cycloheptenones Utilizing a Redox-Relay Heck Strategy

In this report, the desymmetrization of cyclic enones under relay Heck conditions with an array of aryl boronic acids, alkenyl triflates and indole derivatives is described. This method grants facile access to diverse γ-functionalized cyclopentenones and δ-functionalized cycloheptenones. Using this approach, a formal synthesis of (S)-baclofen was completed in high yield and excellent enantioselectivity. (Figure presented.).

Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones

Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.

Platinum-Catalyzed Desaturation of Lactams, Ketones, and Lactones

The development of a general platinum-catalyzed desaturation of N-protected lactams, ketones, and lactones to their conjugated α,β-unsaturated counterparts is reported. The reaction operates under mildly acidic conditions at room temperature or 50 °C. It is scalable and tolerates a wide range of functional groups. The complementary reactivity to the palladium-catalyzed desaturation is demonstrated in the efficient conversion of iodide, bromide, and sulfur-containing substrates.

DIRECT B-ARYLATION OF CARBONYL COMPOUNDS

Disclosed is a method for the β-C—H H functionalization of carbonyl compounds that is both selective and broadly applicable. The methods provide direct β-arylation of carbonyl compound with a diverse array of aryl or heteroaryl halides, aryl or heteroryl tosylate, aryl or heteroaryl triflates, or diaryliodonium salts, by palladium catalysis in the presence of a ligand and promoter.

A highly efficient metal-free approach to: Meta - And multiple-substituted phenols via a simple oxidation of cyclohexenones

A novel and efficient metal-free approach to substituted phenols has been disclosed from simple and readily available cyclohexenones and cyclohexenone equivalents. Dimethyl sulfoxide (DMSO), a simple and common organic reagent, was employed as a mild oxidant in this I2-catalysis, which significantly tolerates various substituents including some easily oxidizable or reducible functionalities. The challenging meta- and multiple-substituted phenols could be well prepared by this method. The metal-free and mild oxidation make this protocol very simple, practical, and easy to handle.

Aerobic double dehydrogenative cross coupling between cyclic saturated ketones and simple arenes

The synthesis of 3-aryl-2-cyclohexenones is a topic of current interest as they are not only privileged structures in bioactive molecules, but they are also relevant feedstocks for the synthesis of substituted phenols or anilines, which are ubiquitous structural elements both in drug design and medicinal chemistry. A simple and sustainable one-pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β-position of cyclic ketones has been developed. Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron-transfer mediators (ETMs) under ambient oxygen pressure. A simple and sustainable one-pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β-position of cyclic ketones has been developed (see scheme). Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron-transfer mediators (ETMs) under ambient oxygen pressure.