74157-93-0

Upstream product

• 65755-95-5 2-phenyl-2-(trimethylsiloxy)-4-hexenal 
• 1617-32-9 (E)-3-pentenoic acid 
• 591-51-5 phenyllithium 
• 84066-62-6 (E)-1-phenyl-1-(2-butenyl)dithiane 
• 1588-56-3 trans-2-phenyl-1-ethylcyclopropane 
• 5425-44-5 2-Phenyl-[1,3]dithiane 
• 80735-94-0 1-Phenyl-3-buten-1-ol 
• 698-16-8 benzohydroximoyl chloride 
• 869572-67-8 2-(1-hydroxyethyl)-1-phenylcyclopropanol 
• 75-11-6 diiodomethane 
• 73172-59-5 [(2RS,3SR)-3-methyloxiran-2-yl]phenylmethanone 
• 4784-77-4 (E)-1-Bromo-2-butene 
• 100-52-7 benzaldehyde 
• 75851-77-3 (E)-1-phenyl-3-penten-1-ol 

Downstream Products

• 75851-77-3 (E)-1-phenyl-3-penten-1-ol 
• 67615-59-2 2,4-dimethyl-1-phenylpent-3-ene-1-one 
• 3592-47-0 Benzaldehyde-d 
• 76620-27-4 4-methyl-N'-((1E,3E)-1-phenylpent-3-en-1-ylidene)benzenesulfonohydrazide 
• 76633-73-3 exo-6-methyl-3-phenyl-1,2-diazabicyclo<3.1.0>hex-2-ene 
• 77764-70-6 (E)-1-phenyl-3-penten-1-one N-tosylhydrazone 

Relevant academic research and scientific papers

Stereoselective synthesis of β,γ-unsaturated ketones by acid-mediated Julia-type transformation from 2-(1-hydroxyalkyl)-1- alkylcyclopropanols

An efficient transformation of 2-(1-hydroxyalkyl)-1-alkylcyclopropanols, obtained from α,β-unsaturated ketones, to β,γ-unsaturated ketones was achieved by trifluoroacetic acid (TFA)-mediated reaction. Georg Thieme Verlag Stuttgart.

Asymmetric Aza-Wacker-Type Cyclization of N-Ts Hydrazine-Tethered Tetrasubstituted Olefins: Synthesis of Pyrazolines Bearing One Quaternary or Two Vicinal Stereocenters

We have developed an asymmetric aza-Wacker-type cyclization of N-Ts hydrazine-tethered tetrasubstituted olefins, affording optically active pyrazolines bearing chiral tetrasubstituted carbon stereocenters. This reaction is tolerant to a broad range of substrates under mild reaction conditions, giving the desired chiral products with high enantioselectivities. Generation of two vicinal stereocenters on the C=C double bonds was also achieved with high selectivities, a process which has been rarely studied for Wacker-type reactions. A mechanistic study revealed that this aza-Wacker-type cyclization undergoes a syn-aminopalladation process. It was also found that for substrates bearing two linear alkyl substituents on the outer carbon atom of the olefin, both of which are larger than a methyl group, the alkyl substituent that is cis to the intranucleophilic group participates more readily in β-hydride elimination. When one of the two alkyl substituents on the outer carbon atom of the olefin is a methyl group, β-hydride elimination proceeds selectively at the methylene side, thus both diastereomers can be prepared via switching the configuration of the olefin. Furthermore, the product can be converted to a pharmaceutical compound in high yields over three steps.

Prins cyclization of α-bromoethers under basic conditions

α-Bromoethers have been found to undergo Prins-type cyclization under basic conditions and without the need to add a promoter. The products are those derived from a Markovnikov addition on the pendant alkene. However, the stereochemistry and even the structure of the products sometimes differ from those expected with the classical Lewis-acid-catalyzed Prins reaction of acetals.

A new zincate-mediated rearrangement reaction of 2-(1-hydroxyalkyl)-1- alkylcyclopropanol

A novel rearrangement of 2-(1-hydroxyalkyl)-1-alkylcyclopropanol has been found. It proceeds in the presence of a catalytic amount of organozinc ate complex to give vic-diols. The rearrangement can be applied to various types of 2-(1-hydroxyalkyl)-1-alkyl-cyclopropanol, which can be easily prepared from the corresponding α,β-ep-oxyketones and bis(iodozincio)methane. When bicyclo[13.1.0]-pentadecane-1, 15-diol was treated with the organozinc ate complex, the corresponding 14-membered cyclic vic-diol was obtained. Thus, this rearrangement is also useful for changing the ring size of cyclic substrates.

Cadmium promoted allylation of acid chlorides: Synthesis of β,γ-unsaturated ketones

A new and efficient method for the preparation of β,γ-unsaturated ketones has been achieved by a simple reaction of an acid chloride with allyl and crotyl bromide and cadmium powder in absolute tetrahydrofuran. Copyright (C) 1996 Published by Elsevier Sci

Hypersensitive radical probe studies of Gif oxidations

Hypersensitive probes were employed in mechanistic studies of Gif oxidations. The results indicate that, unlike the case in enzyme catalyzed hydroxylation reactions, diffusively free radicals are formed in Gif oxidations of these substrates.

Reduction of 4,5-Dihydro-1,2-oxazoles (Δ2-Isoxazolines); A Cycloadditive Approach to 2-Alkenyl Ketones

A new cycloadditive route to 2-alkenyl ketones (β,γ-unsaturated ketones) involves: (1) nitrile oxide-allylsilane (or stannane) cycloaddition, (2) reductive cleavage of the resultant isoxazoline, and (3) Peterson elimination.In all cases, the products are not contaminated by the isomeric 1-alkenyl ketones.Although stereoselectivity in the nitrile oxide cycloaddition to 3-trimethylsilyl-1-butene is low, the resultant diastereomeric cycloadducts can be converted stereospecifically to the corresponding (E)- and (Z)-olefins.

Regiospecific Synthesis of β, γ-Unsaturated Ketones from Allylic Alcohols. Claisen Rearrangement of α-Allyloxy Ketone Enol Derivatives

β,γ-Unsaturated ketones are prepared with regiospecific C-C bond formation at the former γ-position of primary, secondary, or tertiary allylic alcohol precursors by a process involving sigmatropic Claisen rearrangement of intermediate α-allyloxy ket

ON THE MECHANISM AND SYNTHETIC APPLICATIONS OF THE THERMAL AND ALKALINE DEGRADATION OF C-18 CASTOR OIL

The C-18 backbone of castor oil fragments, thermally to C-11 + C-7 by a ?2s + ?2s + ?2s process and with hot alkali to C-10 + C-8 via unique sequence involving a primary reaction which is associated with three different types of redox systems as well as with uncoupled oxidation, the overall change amounting to a milieu of hydride transfer, ?-migration, retro-Michael, retro-aldol, Meerwein-Pondorff-Verley as well as Cannizzaro type of reactions.These findings which constitute the core of the present work, are of significance, not only with respect to the understanding of two of the most important reactions of castor oil, but also in the utilization of this knowledge to channelize and optimize the products desired.Further, they add a distinct facet to mechanistic organic chemistry.Convincing evidence for the concerted nature of the C-18 -> C11 + C7 change of castor oil is the clean transformation of methyl 12-hidroxy octadec 9-ynoate to the novel and useful allenic ester, methyl undeca 9,10-dienoate.Model studies with diversely α-substitued γδ-unsaturated alcohols have shown that the ?2s + ?2s +?2s (retroene) process is assisted by a Cβ α polarization.The utility of the retro-ene reaction of γδ-unsaturated alcohols has been demonstrated with a novel procedure for the PhCHO -> PhCOD change.The mechanism proposed in the present work for the C-18 -> C-10 + C-8 change castor oil whithot alkali provides a rationale for the formation of products at diverse redox levels.In the present work, the mechanism of the complex processes associated with the hot alkali fragmentation of castor oil has been probed using "castor soap", a standard recipe for which has been developed.Neat castor soap decomposes above 240 deg C to give, hydrogen gas (!), 2-octanol (49percent), 2-octanone (24percent) and sebacic acid (12percent).A very noteworthy finding was that the course of the above can be changed by the addition of external redox acceptors whereby the formation of 2-octanol and hydrogen are suppressed.Thus, non-enolizable ketones are reduced whit castor soap tetraphenylcyclopentadiene (12percent) + tetraphenylcyclopenteneone (35percent); fluorenone -> fluorene (34percent); benzophenone -> benzhydrol (44percent)>, hydrazones are converted to hydrocarbons fluorene (70percent); benzophenone hydrazone -> diphenylmethane (50percent)> and, even with calculated quantities of castor soap, amounting to the required 6e transfer, excellent yields (81-95percent) of aromatic amines were obtained from a variety of aromatic nitro compounds.The easily avaiable castor soap has good practical potential.Additionally, the delineation of the multifacetted pathways associated with the castor oil -> sebacic acid change with hot alkali could be used to advantage to optimize conditions relating to products at diverse redox levels, the redox partners could be changed and the theme of co-existence of several redox systems could be transplanted to other substrated.

Silyl Phosphites. XVIII. Versatile Utility of α-(Trimethylsilyloxy)-alkylphosphonates as Key Intermediates for Transformation of Aldehydes into Several Carbonyl Derivatives

Carbonyl addition compounds of diethyl trimethylsilyl phosphite (DTMSP) with aldehydes were converted, by treatment with lithium diisopropylamide (LDA) followed by the successive alkylation and alkaline hydrolysis, to carbonyl derivatives involving aldehydes, unsymmetrical ketones, β,γ-unsaturated ketones, and carboxylic acids. β-Substituted carboxylic esters and γ-substituted lactones were prepared by use of the carbonyl addition compounds of DTMSP with α,β-unsaturated aldehydes.