106986-16-7

Upstream product

• 1145-92-2 (1SR,2SR)-phenyl(2-phenylcyclopropyl)ketone 
• 74-88-4 methyl iodide 
• 71-43-2 benzene 
• 100-42-5 styrene 
• 93-55-0 1-phenyl-propan-1-one 
• 768-56-9 4-Phenylbut-1-ene 
• 93-97-0 benzoic acid anhydride 
• 864517-26-0 1,4-diphenyl-2-methyl-2-buten-1-one 
• 611-70-1 phenyl isopropyl ketone 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 2344-70-9 1-phenyl-3-butanol 
• 59456-20-1 (rac)-(3-iodobutyl)benzeze 
• 13939-06-5 molybdenum hexacarbonyl 
• 98-80-6 phenylboronic acid 

Downstream Products

• 100-42-5 styrene 
• 93-55-0 1-phenyl-propan-1-one 
• 106986-22-5 (2R,2'S),(E/Z)-O-<2'-methoxy-2'-(trifluoromethyl)phenylacetyl>-1,4-diphenyl-2-methylbutan-1-one oxime 
• 106986-22-5 (2S,2'S),(E/Z)-O-<2'-methoxy-2'-(trifluoromethyl)phenylacetyl>-1,4-diphenyl-2-methylbutan-1-one oxime 
• 106986-18-9 (2R),(E/Z)-1,4-diphenyl-2-methylbutan-1-one oxime 
• 858942-14-0 2-methyl-1,4-diphenylbutan-1-ol 
• 858942-11-7 2,5-diphenyl-3-methylpent-1-ene 
• 876062-11-2 C₁₇H₁₉Cl 

Relevant academic research and scientific papers

Cobalt-Catalyzed Markovnikov-Selective Radical Hydroacylation of Unactivated Alkenes with Acylphosphonates

Acylphosphonates having the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton are developed as efficient intermolecular radical acylation reagents, which enable the cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature under mild conditions. The protocol exhibits broad substrate scope and wide functional group compatibility, providing branched ketones in satisfactory yields. A mechanism involving the Co-H mediated hydrogen atom transfer and subsequent trapping of alkyl radicals by acylphosphonates is proposed.

Reductive C-C Coupling by Desulfurizing Gold-Catalyzed Photoreactions

[Au2(μ-dppm)2]Cl2-mediated photocatalysis reactions are usually initiated by ultraviolet A (UVA) light; herein, an unreported system using blue light-emitting diodes (LEDs) as excitation light source was found. The red shift of the absorption wavelength originates from the combination of [Au2(μ-dppm)2]Cl2 and ligand (Ph3P or mercaptan). On the basis of this finding, a gold-catalyzed reductive desulfurizing C-C coupling of electrophilic radicals and styrenes mediated by blue LEDs is presented, a coupling which cannot be efficiently accessed by previously reported methods. This mild and highly efficient C-C bond formation strategy uses mercaptans both as electron-deficient alkyl radical precursor as well as the hydrogen source. Two examples of amino acids have also been modified by using this strategy. Moreover, this methodology could be applied in polymer synthesis. Gram-scale synthesis and mechanistic insights into this transformation are also presented.

Iron-Catalysed Remote C(sp3)?H Azidation of O-Acyl Oximes and N-Acyloxy Imidates Enabled by 1,5-Hydrogen Atom Transfer of Iminyl and Imidate Radicals: Synthesis of γ-Azido Ketones and β-Azido Alcohols

In the presence of a catalytic amount of iron(III) acetylacetonate [Fe(acac)3], the reaction of structurally diverse ketoxime esters with trimethylsilyl azide (TMSN3) afforded γ-azido ketones in good to excellent yields. This unprecedented distal γ-C(sp3)?H bond azidation reaction went through a sequence of reductive generation of an iminyl radical, 1,5-hydrogen atom transfer (1,5-HAT) and iron-mediated redox azido transfer to the translocated carbon radical. TMSN3 served not only as a nitrogen source to functionalise the unactivated C(sp3)?H bond, but also as a reductant to generate the catalytically active FeII species in situ. Based on the same principle, a novel β-C(sp3)?H functionalisation of alcohols via N-acyloxy imidates was subsequently realised, leading, after hydrolysis of the resulting ester, to β-azido alcohols, which are important building blocks in organic and medicinal chemistry.

Palladium and visible-light mediated carbonylative Suzuki-Miyaura coupling of unactivated alkyl halides and aryl boronic acids

Herein, a simple and efficient method for the palladium-catalyzed carbonylation of aryl boronic acids with unactivated alkyl iodides and bromides under visible-light irradiation, ambient temperature and low CO-pressure is presented. Notably, the procedure uses readily available equipment and an inexpensive palladium catalyst to generate the key alkyl radical intermediate. These mild conditions enabled the synthesis of a range of functionalized aryl alkyl ketones including the antipsychotic drug, melperone.

KOtBu-Mediated Domino Isomerization and Functionalization of Aromatic Allylic Alcohols

Transition-metal- as well as ligand-free base-mediated domino isomerization and alkylation of allylic alcohols is presented. This protocol features the conversion of simple allylic alcohols into the corresponding ketones through isomerization in the presence of a simple base. Significantly, these in situ generated ketones subsequently undergo alkylation with styrenes as electrophiles, in a domino one-pot fashion, as an atom- and step-economical chemical process.

Stereospecific Palladium-Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions

We report the development of a Pd-catalyzed process for the cross coupling of unactivated primary, secondary, and tertiary alkylcarbastannatrane nucleophiles with acyl electrophiles. Reactions involving optically active alkylcarbastannatranes occur with exceptional stereofidelity and with net retention of absolute configuration. Because the stereochemistry of the resulting products is entirely reagent-controlled, this process may be viewed as a general, alternative approach to the preparation of products typically accessed via asymmetric enolate methodologies. Additionally, we report a new method for the preparation of optically active alkylcarbastannatranes, which should facilitate their future use in stereospecific reactions.

Cu(I)-catalyzed α-alkylation of ketones with styrene derivatives

α-Alkylation of ketones with styrene derivatives was developed using a mesitylcopper-dppp complex as a soft Bronsted base catalyst. No waste derived from the alkylating reagent was produced in this catalytic alkylation reaction. The bisphosphine ligand structure, as well as the reaction solvent, had profound effects on catalyst activity. The reaction proceeded under mild conditions from a range of ketones and styrene derivatives. The present catalysis is especially useful for the selective mono-alkylation of ketones.

Intramolecular O-H...O hydrogen-bond-mediated reversal in the partitioning of conformationally restricted triplet 1,4-biradicals and amplification of diastereodifferentiation in their lifetimes

The photoreactivity and nanosecond transient phenomena have been investigated for a rationally designed set of ketones 4-9 in order to gain comprehensive insights concerning the influence of intramolecular hydrogen bonding on (i) the lifetimes of triplet 1,4-biradicals and (ii) the partitioning of the latter between cyclization and elimination. Comparisons of the photochemical results and lifetime data for the biradicals of ketones 6 versus 8 and 7 versus 9 revealed a remarkable influence of hydrogen bonding when superimposed upon steric factors: while 6 and 7 yielded cyclobutanols in poor yields, cyclization was found to be overwhelmingly predominant for 8-anti and moderately so for 9-anti, with a high stereoselectivity in the formation of cyclobutanols (>95% for 8-anti). The diastereochemistry in the case of 8 permitted the occurrence of fragmentation or cyclization almost exclusively (>90% cyclization for 8-anti and >75% elimination for 8-syn). Significantly, the intramolecular hydrogen bonding in the biradicals of 8 and 9 was found to reverse their partitioning between cyclization and elimination compared with the behavior of the biradicals of ketones 3; the ketones 8-anti and 9-anti underwent cyclization in benzene, predominantly leading to cyclobutanols with syn stereochemistry between the C2 and C3 substituents. In accordance with photoproduct profiles, an unprecedented ～2-fold difference in the lifetimes of the intermediate diastereomeric triplet biradicals of ketones 8 in nonpolar solvents (e.g., τsyn = 123 ns and τanti = 235 ns in cyclohexane) was observed via nanosecond laser flash photolysis, while no such difference in lifetimes was found for the triplet biradicals of acetoxy ketones 9. The intriguing diastereodifferentiation in the lifetimes of the diastereomeric triplet 1,4-biradicals of 8 and the product profiles of ketones 6, 7, and 9 are best reconciled via a unified mechanistic picture in which superposition of steric factors over varying magnitudes of O-H...O hydrogen bonding selectively facilitates a particular pathway. In particular, the diastereodifferentiation in the photochemical outcomes for the diastereomers of ketone 8 and in the lifetimes of their triplet biradicals can be understood on the basis of rapid deactivation of the 8-syn triplet biradical via fragmentation and slow cyclization of the 8-anti triplet biradical from chair- and twist-boat-like hydrogen-bonded conformations, respectively. The photolysis in polar aprotic solvents such as DMSO and pyridine was found to reverse the chemoselectivity, yielding reactivity paralleling that of ketones 3, for which the steric factors between the C2 and C3 substituents control the photochemical outcome.

Branch-selective intermolecular hydroacylation: Hydrogen-mediated coupling of anhydrides to styrenes and activated olefins

(Chemical Equation Presented) Branching out with hydrogen: Hydrogenation of symmetric or mixed carboxylic anhydrides in the presence of styrenes or activated olefins generates intermolecular hydroacylation products. The use of cationic rhodium catalysts ligated by triphenylarsine (Ph3As) results in the formation of branched coupling products as single regioisomers in high yields (see scheme; cod = cycloocta-1,5-diene, ArF = 3,5-(CF 3)2C6H3).

Potassium tert-butoxide catalyzed addition of carbonyl derivatives to styrenes

(matrix presented) A catalytic amount of t-BuOK in DMSO allows the addition of ketones or imines to styrenes at 40 °C in good to excellent yield. Nitriles add to styrenes in NMP or in DMSO at room temperature.