74207-62-8

Upstream product

• 1195-32-0 1-methyl-4-isopropenylbenzene 
• 1197-01-9 p-cymene-8-ol 
• 68-12-2 N,N-dimethyl-formamide 
• 74207-61-7 3-p-tolyl-2Z-butenal 
• 109-92-2 ethyl vinyl ether 
• 766-97-2 4-n-methylphenylacetylene 
• 123-73-9 crotonaldehyde 
• 18913-31-0 2,3-butadien-1-ol 
• 5720-05-8 4-methylphenylboronic acid 
• 130633-06-6 (E)-3-(4-methylphenyl)-but-2-en-1-ol 
• 6305-61-9 ethyl (E)-3-p-tolylbut-2-enoate 
• 122-00-9 para-methylacetophenone 
• 94853-53-9 ethyl 3-(4-methylphenyl)-2-butenoate 
• 74207-58-2 2-(p-tolyl)but-3-yn-2-ol 

Downstream Products

• 1616761-23-9 (R)-3-bromo-9-(p-tolyl)-10,10a-dihydro-6H-benzo[c]chromen-6-one 
• 80352-30-3 (E)-4-(p-tolyl)-3-penten-2-one 
• 151765-65-0 (S)-3-(4-methylphenyl)butanal 
• 104598-15-4 (R)-3-(4-methylphenyl)butanal 
• 80352-31-4 (E)-4-p-Tolyl-pent-3-en-2-ol 

Relevant academic research and scientific papers

Stereodefined rhodium-catalysed 1,4-H/D delivery for modular syntheses and deuterium integration

Deuterium-incorporated compounds are of high interest owing to their importance in the pharmaceutical industry, organic synthesis and materials science. So far, the integration of deuterium into the inert, saturated magic methyl or methylene groups of covalent molecules remains challenging. Here, we present a 1,4-H delivery of allylic metallic species to provide a highly stereoselective and straightforward approach to 3-methyl-2(E)-enals or -enones from readily available 2,3-allenols and organoboronic acids. The reaction accommodates many synthetically versatile functional groups as well as multi-pharmacophores, and is not limited to the formation of 3-methyl derivatives. By applying 1,4-H or D delivery, deuterium atom(s) from differently deuterated allenols can be edited into the methyl or methylene groups of versatile organic skeletons, resulting in the efficient formation of 4-monodeuterated, 1,4- and 4,4-doubly deuterated, and 4,4,4-triply deuterated 2(E)-enals or -enones. These powerful platform molecules can provide straightforward paths to other deuterated compounds for different purposes. [Figure not available: see fulltext.].

Preparation method for cinnamaldehyde and derivatives thereof

The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method for cinnamaldehyde and derivatives thereof. The preparation method includes taking styrene or derivatives thereof as a substrate, reacting the substrate with a formamide solvent, iodoform and alkali at a certain temperature and under the protection of argon, and completing carbonylation to generate target products, namely the cinnamaldehyde and the derivatives thereof. The preparation method of the cinnamaldehyde and the derivatives thereof has the advantages of low cost and easyavailability of raw materials, no metal catalysis, environmental friendliness, high reaction yield and the like, thereby having a good industrial application prospect.

Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon Stereocenters via Functionalization of 1,3-Dienes with CO2

The catalytic asymmetric functionalization of readily available 1,3-dienes is highly important, but current examples are mostly limited to the construction of tertiary chiral centers. The asymmetric generation of acyclic products containing all-carbon quaternary stereocenters from substituted 1,3-dienes represents a more challenging, but highly desirable, synthetic process for which there are very few examples. Herein, we report the highly selective copper-catalyzed generation of chiral all-carbon acyclic quaternary stereocenters via functionalization of 1,3-dienes with CO2. A variety of readily available 1,1-disubstituted 1,3-dienes, as well as a 1,3,5-triene, undergo reductive hydroxymethylation with high chemo-, regio-, E/Z-, and enantioselectivities. The reported method features good functional group tolerance, is readily scaled up to at least 5 mmol of starting diene, and generates chiral products that are useful building blocks for further derivatization. Systemic mechanistic investigations using density functional theory calculations were performed and provided the first theoretical investigation for an asymmetric transformation involving CO2. These computational results indicate that the 1,2-hydrocupration of 1,3-diene proceeds with high π-facial selectivity to generate an (S)-allylcopper intermediate, which further induces the chirality of the quaternary carbon center in the final product. The 1,4-addition of an internal allylcopper complex, which differs from previous reports involving terminal allylmetallic intermediates, to CO2 kinetically determines the E/Z- and regioselectivity. The rapid reduction of a copper carboxylate intermediate to the corresponding silyl-ether in the presence of Me(MeO)2SiH provides the exergonic impetus and leads to chemoselective hydroxymethylation rather than carboxylation. These results provide new insights for guiding further development of asymmetric C-C bond formations with CO2

Gold catalyzed Heck-coupling of arenediazonium o-benzenedisulfonimides

Diazonium salts, and precisely arenediazonium o-benzenedisulfonimides, have been used for the first time as efficient electrophilic partners in gold catalyzed Heck-coupling reactions. The synthetic protocol was general, easy and gave the target products in satisfactory yields. Mechanistic insights revealed the fundamental roles of the o-benzenedisulfonimide anion as an electron transfer agent thath promotes a radical pathway that does not require the presence of photocatalysts or external oxidants.

Rh-Catalyzed Asymmetric Hydrogenation of β-Branched Enol Esters for the Synthesis of β-Chiral Primary Alcohols

An asymmetric hydrogenation of β-branched enol esters has been developed for the first time, providing a new route for the synthesis of β-chiral primary alcohols. Using a (S)-SKP-Rh complex bearing a large bite angle and enol ester substrates possessing an O-fomyl directing group, the desired products were obtained in quantitative yields and with excellent enantioselectivities.

Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Scope and Mechanistic Studies

Although iminium catalysis has become an important tool in organic chemistry, its combination with supramolecular host systems has remained largely unexplored. We report the detailed investigations into the first example of iminium catalysis inside a supramolecular host. In the case of 1,4-reductions of α,β-unsaturated aldehydes, catalytic amounts of host are able to increase the enantiomeric excess of the products formed. Several control experiments were performed and provided strong evidence that the modulation of enantiomeric excess of the reaction product indeed stems from a reaction on the inside of the capsule. The origin of the increased enantioselectivity in the capsule was investigated. Furthermore, the substrate and nucleophile scope were studied. Kinetic investigations as well as the kinetic isotope effect measured confirmed that the hydride delivery to the substrate is the rate-determining step inside the capsule. The exploration of benzothiazolidines as alternative hydride sources revealed an unexpected substitution effect of the hydride source itself. The results presented confirm that the noncovalent combination of supramolecular hosts with iminium catalysis is opening up new exciting possibilities to increase enantioselectivity in challenging reactions.

Iminium Catalysis inside a Self-Assembled Supramolecular Capsule: Modulation of Enantiomeric Excess

The noncovalent combination of a supramolecular host with iminium organocatalysis is described. Due to cation–π interactions the reactive iminium species is held inside the host and reacts in this confined environment. The products formed differ up to 92 % ee from the control experiments without added host. A model rationalizing the observed difference is presented.

Ruthenium-catalyzed oxidation of allyl alcohols with intermolecular hydrogen transfer: Synthesis of α,β-unsaturated carbonyl compounds

Ruthenium-catalyzed oxidation of multisubstituted allyl alcohols in the presence of benzaldehyde gives enals or enones in good yields. Unlike the commonly reported ruthenium-catalyzed isomerization reaction of allyl alcohols to give saturated ketones, an intermolecular rather than intramolecular hydrogen transfer is involved in this transformation. This reaction offers an efficient, mild, and high-yielding method for the preparation of substituted α,β-unsaturated compounds.

Alkyne-enol ether cross-metathesis in the presence of CuSO4: Direct formation of 3-substituted crotonaldehydes in aqueous medium

An efficient synthesis of 3-substituted crotonaldehydes via alkyne-enol ether cross-metathesis in the presence of CuSO4 and in aqueous medium was developed. Crotonaldehydes were obtained in good yields from terminal aryl-alkynes as well as from

Baker's yeast mediated enantioselective synthesis of the bisabolane sesquiterpenes curcumene, turmerone, dehydrocurcumene and nuciferal

Fermenting baker's yeast converts the allylic alcohol 6 into enantiomerically pure (S)-(+)-3-(p-tolyl)butan-1-ol 7 which is a useful chiral building block for the synthesis of bisabolane sesquiterpenes. The versatility of this approach is shown in the preparation of (S)-(+)-curcumene, (S)-(+)-turmerone, (S)-(+)-dehydrocurcumene and (E,S)-(+)-nuciferal.