95062-99-0

Upstream product

• 101100-11-2 1-(3-phenylpropyl)cyclohexanol 
• 3277-89-2 phenethylmagnesium bromide 
• 33867-02-6 1-chloromethylcyclohexene 
• 4119-41-9 1-iodo-3-phenylpropan 
• 28075-50-5 cyclohex-1-en-1-yl trifluoromethane sulfonate 
• 2046-33-5 3-methoxypropylbenzene 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 1633-79-0 5-Mercapto-1-pentanol 
• 104-52-9 phenylpropyl chloride 
• 637-59-2 1-Bromo-3-phenylpropane 
• 42808-98-0 phenethyllithium 
• 167389-29-9 (S)-N-methyl-S-(1-cyclohexen-1-ylmethyl)-S-phenylsulfoximine 

Relevant academic research and scientific papers

Ni-catalyzed cross-electrophile coupling between vinyl/aryl and alkyl sulfonates: Synthesis of cycloalkenes and modification of peptides

We report here the coupling reactions between vinyl/aryl and alkyl C-O electrophiles that can be derived from chemical feedstocks and naturally occurring functional groups. This method provides an efficient approach to the synthesis of a wide range of fun

Synthesis of cyclic olefins via Mitsunobu C-alkylation followed by Ramberg-B?cklund ring contraction

Cyclic olefins were prepared via a novel synthetic approach that involves the formation of two C–C bonds in a potentially stereoselective fashion. The first bond is formed by employing a Mitsunobu dehydrative C-alkylation; the second C–C bond involves a ring contraction via Ramberg-B?cklund rearrangement.

Stereospecific Ni-catalyzed cross-coupling of potassium alkenyltrifluoroborates with alkyl halides

A general method for the alkenylation of alkyl electrophiles using nearly stoichiometric amounts of the air- and moisture-stable potassium organotrifluoroborates has been developed. Various functional groups were tolerated on both the nucleophilic and electrophilic partner. Reactions of highly substituted E- and Z-alkenyltrifluoroborates, as well as vinyl- and propenyltrifluoroborates, were successful, and no loss of stereochemistry or regiochemistry was observed.

β- and γ-disubstituted olefins: Substrates for copper-catalyzed asymmetric allylic substitution

The copper-catalyzed asymmetric allylic alkylation has shown through many examples that it is a powerful means to generate stereogenic centers with mono β- and γ-substituted olefinic substrates. However, little has been reported about more substituted olefinic patterns, such as β-disubstituted allylic electrophiles. In this paper, we show that a simple procedure using easily accessible Grignard reagents and as low as 3 mol% of copper/ligand can promote high to nearly perfect enantioselectivities (up to >99% ee) with very good γ-selectivities on a wide panel of aliphatic or aromatic β-disubstituted substrates.

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).

Regio- and enantioselective substitution of primary endocyclic allylic sulfoximines with organocopper and organocuprate reagents. The importance of iodide for the allylic substitution with organocopper compounds

The endocyclic N-substituted allylic sulfoximines 17-20 and 26 were synthesized from the corresponding cycloalkanones and the various (S)-5-(lithiomethyl)-S-phenylsulfoximines in enantiomerically pure form in yields of 60-70% in a process involving the isomerization of the intermediate vinylic sulfoximines. Desilylation of 26 gave the parent N-H sulfoximine 27 from which the N-sulfonylsulfoximines 28 and 29 were prepared. The X-ray crystal structure of 28 was determined. The allylic sulfoximines 17-20 and 26-29 did not racemize or rearrange thermally to the corresponding allylic sulfinamides. Reaction of the allylic sulfoximines 18, 28, and 29 with the organocuprate reagents 2/LiI, 35/LiI, and 47/LiI led with α-selectivities of 92:8 to 99:1 to the endocyclic alkenes 39 in good to high yields. Reaction of 17-20, 28, and 29 with the organocopper reagents 5/LiI, 30/LiI, 31/LiI, 32/LiI, 33/LiI, 34/LiI, and 37/LiI in the presence of BF3 resulted in the formation of the exocyclic alkenes 38, 41, 43, and 45, respectively, in good to high yields with γ-selectivities of 80:20 to 99:1. The sulfonimidoyl group imparts asymmetric induction to the substitution in the range of 27-90% ee. The (S)-sulfonimidoyl group leads to a preferential bond formation from the si side of the double bond. From the sulfoximines 18 and 26-29 the N-methylsulfoximine 18 and the N-tosylsulfoximine 28 showed the highest and lowest reactivity with the butylcopper reagent 32/LiI in the presence of BF3, respectively, while in the absence of BF3 only 29 reacted. The Lewis acid most likely serves to activate the N-methyl- and N-tosylsulfoximines or intermediates thereof through coordination at the sulfonimidoyl and sulfonyl group. Reaction of the sulfoximines 18 and 29 with pure Me3SiCH2Cu (34) revealed a strong rate acceleration by LiI and an even stronger one by Bu4NI. This points to the existence of a heteroleptic cuprate or a related compound as reactive species. In substitutions with the Yamamoto reagents RCu/MX/BF3, the halide is important and a reaction between RCu and BF3 does not have, at least in the case of allylic sulfoximines, to be invoked. In reactions of 17-20 besides the alkenes, the sulfinamide ent-4 was formed with an ee value of 97% in high yield with retention of configuration. The absolute configuration of the exocyclic alkenes 38, 41, and 45 was determined by ozonolysis to the corresponding cycloalkanones followed by their conversion to the corresponding lactones and/or CD measurement of the former.

Substituent Effects on the Intramolecular Photochemical Reactions of Phenyl-Ethenyl Non-conjugated Bichromophoric Systems

The effects of substitution on the photochemistry of phenyl-ethenyl bichromophoric systems are reported.Methyl substitution at the 2-, 3-, 5-, and 1,1,2-positions in the pentene moiety of 5-phenylpent-1-ene reduces both reaction efficiency and selectivity but in contrast to intramolecular analogues the photoreaction of 3-phenethylcyclohexene is comparable with that of the corresponding cyclopentene.Incorporation of ester units in the connecting unit between the chromophores or on the ethene inhibits intramolecular cyclisation as does the presence of para OMe, CN, or COMe groups in 5-phenylpent-1-ene.In contrast reaction selectivity and efficiency are greatly promoted by ortho Me or OMe groups and the products reflect exlusive 1,3-cycloaddition.The presence of a para Me group in 5-phenylpent-1-ene leads to specific 2,6-intramolecular cyclisation but the reaction of the meta-Me derivative leads to four products derived from 1,3- and 1,5-intramolecular cycloaddition.The observations are discussed in terms of mechanisms of arene-ethene photoreactions and preferred conformations of the bichromophores.