103305-31-3

Upstream product

• 131469-72-2 methyl 3-acetoxy-3-(4-chlorophenyl)-2-methylenepropanoate 
• 24654-54-4 3-(4-chlorophenyl)-2-methylpropenal 
• 1202-60-4 -2-methyl-3-(4-chlorophenyl)prop-2-enoic acid 
• 104-88-1 4-chlorobenzaldehyde 
• 92576-43-7 ethyl 3-(4-chlorophenyl)-2-methyl-2-propenoate 
• 50-00-0 formaldehyd 
• 2809-65-6 4-chloro-1-propynylbenzene 

Downstream Products

• 24654-54-4 3-(4-chlorophenyl)-2-methylpropenal 
• 103305-43-7 (2S,3S)-3-(4-Chloro-phenyl)-2,4-dimethyl-pent-4-enoic acid ethyl ester 
• 103305-43-7 (2R,3S)-3-(4-Chloro-phenyl)-2,4-dimethyl-pent-4-enoic acid ethyl ester 

Relevant academic research and scientific papers

Asymmetric Nazarov Cyclizations of Unactivated Dienones by Hydrogen-Bond-Donor/Lewis Acid Co–Catalyzed, Enantioselective Proton-Transfer

We report an enantioselective Nazarov cyclization catalyzed by chiral hydrogen-bond-donors in concert with silyl Lewis acids. The developed transformation provides access to tri-substituted cyclopentenones in high levels of enantioselectivity (up to 95% e.e.) from a variety of simple unactivated dienones. Kinetic and mechanistic studies are consistent with a reversible 4π-electrocyclization C?C bond-forming step followed by rate- and enantio-determining proton-transfer as the mode of catalysis. (Figure presented.).

Copper-Catalyzed Stereospecific Hydroboration of Internal Allylic Alcohols

An effective Cu-catalyzed stereospecific hydroboration of aliphatic and aromatic 1,1,2-trisubstituted internal allylic alcohols has been reported. This reaction proceeds via a silyl ether transient protection of allylic alcohols and subsequent stereospecific hydroboration. Followed by an oxidative workup, an array of acyclic, cyclic, and heterocyclic 1,3-diols was synthesized in good to excellent yields with good functional group tolerance and excellent diastereomeric ratios (> 20:1).

Highly enantioselective hydrogenation of 2-substituted-2-alkenols catalysed by a ChenPhos-Rh complex

Highly enantioselective hydrogenation of a variety of 2-substituted-2- alkenols has been achieved using a ChenPhos-Rh complex as catalyst, giving ≥99% ee for most substrates. Optically active antifungal agent amorolfine was first synthesised using hydrogenation as the key step. This journal is

Divergent regioselectivity in the synthesis of trisubstituted allylic alcohols by nickel- and ruthenium-catalyzed alkyne hydrohydroxymethylation with formaldehyde

Stoichiometric metals banned: Nonsymmetrically disubstituted alkynes were converted into primary trisubstituted allylic alcohols upon exposure to paraformaldehyde in the presence of nickel or ruthenium catalysts, which exhibit complementary regioselectivity and complete stereoselectivity in the absence of exogenous reducing agents (see scheme). Copyright

An organocatalytic asymmetric nazarov cyclization

An organocatalytic asymmetric Nazarov cyclization of diketoesters that proceeds by means of a dual activation mechanism has been developed. Screening of a number of catalysts led to a new thiourea that incorporates a primary amino group. The method gives rise to cyclic products with two adjacent quaternary asymmetric carbon atoms, one of which is an all-carbon stereocenter, with complete or nearly complete diastereoselectivity and in high or very high enantiomeric excess. A brief and very convenient synthesis of the acyclic diketoester starting materials through nucleophilic addition to a ketene is also described.

β-disubstituted allylic chlorides: Substrates for the Cu-catalyzed asymmetric SN2′ reaction

Scope broadened: A previously developed asymmetric Cu-catalyzed allylic substitution can be applied to more substituted allylic patterns. Two classes of β-disubstituted substrates, cinnamyl derivatives and aliphatic endocyclic allylic chlorides, afford excellent regio- and enantioselectivities (see schemes; L* = phosphoramidite ligand). (Chemical Equation Presented).

A Study of Enantioselective Reduction of para-Substituted 2-Methyl-cinnamaldehydes by Baker's Yeast

Reduction of a series of para-substituted 2-methyl-cinnamaldehydes (1-7) at 20°C and at pH = 2-3 afforded S-enantiomers of saturated alcohols 8-14 in 20-80% yield and 75 - ≥ 99% enantiomeric excess (e.e.); at 30°C, lower yields and e.e.s were obtained. Relative rates of the formation of allylic alcohols 15-21, catalyzed by alcohol dehydrogenase (ADH), correlate with the Hammett σ+ values of para-substituents, revealing that a more efficient delocalization of the positive charge on carbonylic carbon slow down the reduction rates, whereas no correlation of the electronic properties of the substituents with the rate of C=C double bond reduction, catalyzed by enoate reductase, is observed. On reduction of 3 by dried yeast in 2H2O, α,β-carbon atoms in 10a bear 2H atoms, in accordance with the previously reported hydrogenation of selectively 2H-labeled cinnamic aldehyde and cinnamic alcohol. The accumulated data indicate that the mechanism of the enone C=C bond reduction that comprises nucleophilic attack of the hydride ion species on the β-carbon in the first step, followed by enantioselective protonation on the α-carbon atom.

Pesticidal cyclopropyl-2,4-dieneamides

The present Application discloses pesticidally active compounds of the formula (I): or a salt thereof, wherein Q is an monocyclic aromatic ring. or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one may be nitrogen and the rest carbon each optionally substituted, or Q is a dihalovinyl group or a group R6 --C C-- where R6 is C1-4 alkyl, tri C1-4 alkylsilyl, halogen or hydrogen; Q1 is a 1,2-cyclopropyl ring optionally substituted by one or more groups selected from C1-3 alkyl. halo, C1-3 haloalkyl, alkynyl, or cyano; R2,R3, R4 and R5 are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo. C1-4 alkyl or C1-4 haloalkyl; X is oxygen or sulphur; and R1 is selected from hydrogen and C1-8 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy. their preparation, pesticidal compositions containing them and their use against pests.

Applications of Baylis-Hillman Coupling Products: a Remarkable Reversal of Stereochemistry from Esters to Nitriles: a Simple Synthesis of (2E)-2-Methylalk-2-en-1-ols and (2Z)-2-Methylalk-2-enenitriles

Reaction of methyl 3-acetoxy-2-methylenealkanoates with the reducing agent, lithium aluminium hydride (LAH): ethanol (1:1), provides (2E)-2-methylalk-2-en-1-ols, whereas, reaction of 3-acetoxy-2-methylenealkanenitriles with the same reagent provides (2Z)-2-methylalk-2-enenitriles in high yields.