110474-44-7

Upstream product

• 7129-41-1 6-oxabicyclo[3.1.0]hex-2-ene 
• 934-56-5 trimethyl(phenyl)stannane 
• 6638-68-2 4,5-dimethyl-2-phenyl-1,3,2-dioxaborolane 
• 61740-26-9 cis-3-acetoxy-5-hydroxycyclopent-1-ene 
• 591-50-4 iodobenzene 
• 96-09-3 styrene oxide 
• 108-86-1 bromobenzene 
• 591-51-5 phenyllithium 
• 130792-58-4 Chloro-acetic acid (1R,4S)-4-hydroxy-cyclopent-2-enyl ester 
• 100-58-3 phenylmagnesium bromide 
• 188637-54-9 cyclopent-4-ene-1,3-diyl diethyl dicarbonate 
• 98-80-6 phenylboronic acid 
• 152293-92-0 tert-Butyl-((E)-5-chloro-2-phenyl-pent-3-enyloxy)-dimethyl-silane 
• 152293-78-2 (E)-5-(tert-Butyl-dimethyl-silanyloxy)-4-phenyl-pent-2-en-1-ol 

Downstream Products

• 42086-64-6 trans-2-phenylcyclopentan-1-ol 

Relevant academic research and scientific papers

Ligand-controlled selectivity in the desymmetrization of meso cyclopenten-1,4-diols via rhodium(I)-Catalyzed addition of arylboronic acids

A highly enantioselective desymmetrization of meso cyclopent-2-ene-1,4- diethyl dicarbonates has been developed using a Rh-catalyzed asymmetric allylic substitution. Depending on the type of ligand used, each of two regioisomeric products can be obtained in good yield and excellent enantioselectivity. Under rhodium(I) catalysis, bisphosphine P-Phos ligands form trans-1,2- arylcyclopentenols as the major product, whereas Segphos ligands lead predominantly to trans-1,4-arylcyclopentenols.

Copper-catalyzed γ-selective and stereospecific allyl-aryl coupling between (Z)-acyclic and cyclic allylic phosphates and arylboronates

A Cu-catalyzed allyl-aryl coupling reaction between (Z)-acyclic or cyclic allylic phosphates and arylboronates proceeds with excellent γ-E-selectivity and 1,3-anti chirality transfer, which gives the corresponding coupling products with benzylic and allylic stereogenic centers. The wide availability and easy-to-handle nature of arylboronates, the inexpensiveness of the Cu catalyst system, and the high regio- and stereoselectivities are attractive features of this protocol.

Realization of anti-SN2′ selective allylation of 4-cyclopentene-1,3-diol monoester with aryl- and alkenyl-zinc reagents

(Chemical Equation Presented) Anti-SN2′ mode of allylation of the monoester of 4-cyclopentene-1,3-diol with aryl and alkenyl anions was achieved, for the first time, with the MeOCH2CO2- group as a leaving group to which R-ZnBr and CuCl (as a catalyst) were best fitted. The aryl groups successfully installed were Ph, o- and p-MeC6H 4, o-MOMOC6H4, o-MeOC6H4, and p-F-C6H4, while cis and trans alkenyl groups were attached with retention of the olefinic stereochemistries.

Rhodium-catalysed substitutive arylation of cis-allylic diols with arylboroxines

Substitutive arylation of cis-allylic diols occurs upon treatment with arylboroxines in the presence of a rhodium(i) catalyst; the reaction proceeds through the addition of an intermediate arylrhodium(i) species across the carbon-carbon double bond and su

New reagent system for attaining high regio- and stereoselectivities in allylic displacement of 4-cyclopentene-1,3-diol monoacetate with aryl- and alkenylmagnesium bromides

(Chemical Equation Presented) Low regioselectivity of RMgBr (R = aryl, alkenyl) in the CuCN-catalyzed reaction with 4-cyclopentene-1,3-diol monoacetate is improved by addition of LiCl or MgCl2 to a similar extent as previously obtained with RMg

Aryl- and alkenyllithium preparations and copper-catalyzed reaction between the derived magnesium reagents and the monoacetate of 4-cyclopentene-1,3-diol

(Chemical Equation Presented) Aryl- and alkenyllithiums, prepared by halogen-lithium exchange with lithium, exchange with n-(or t-)BuLi, stannane-lithium exchange with n-BuLi, and direct lithiation with n-BuLi, were transformed into magnesium reagents wit

A new reagent system for installation of an aryl group onto the monoacetate of 4-cyclopentene-1,3-diol

Among the three types of reagents from PhMgX (X=Br, Cl) and CuCN for phenylation of 4-cyclopentene-1,3-diol monoacetate, PhMgCl/CuCN (cat.) and Ph2Cu(CN)(MgCl)2 in THF afforded the trans-1,4-isomer efficiently (82-87% yields, 91-93% regioselectivity). Similarly, o- and p-RC6H4MgCl (R=Me, OMe, CH2=CH) in combination with CuCN furnished good to excellent reactivity and regioselectivity. As an application, a three-step synthesis of dihydromultifidene was accomplished successfully.

A new method for installation of aryl and alkenyl groups onto a cyclopentene ring and synthesis of prostaglandins

To construct a new strategy for synthesis of cyclopentanoids, the transition metal-catalyzed coupling reaction of cis 4-cyclopentene-1,3-diol monoacetate 1 with hard nucleophiles, RT-m, was investigated (eq 1 in Chart 1). Although preliminary experiments using PhZnCl, PhSnMe3, [Ph-B(Me)(OCH-(Me)CH(Me)O)]-Li+ (6a) (derived from boronate ester 4a (RT = Ph) and MeLi) in the presence of a palladium or a nickel catalyst resulted in production of unidentified compounds, enone 16, and/or ketone 17 or recovery of 1, a new borate 5a (derived from 4a and n-BuLi) in the presence of a nickel catalyst (NiCl2(PPh3)2) in THF at room temperature furnished the trans coupling products 2a (RT = Ph) and 3a (RT = Ph) in high combined yield, but with a low product ratio of 0.9:1. The ratio was improved to 13:1 by addition of t-BuCN and NaI into the reaction mixture. This is the first successful example of the reaction of 1 with a hard nucleophile, and the increase in the ratio, realized with the additives, is unprecedented. This reagent system (borate 5 (1.2-1.8 equiv), NiCl2-(PPh3)2 (5-10 mol%), t-BuCN (2-5 equiv), NaI (0.5-1 equiv), THF, room temp) was further investigated with aryl borates 5b-g and alkenyl borates 5h-n to afford 2b-n in moderate to good yields (52-89%) with practically acceptable levels of the regioselectivity (5 ～ 21:1), thus establishing the generality of the reaction (Table 2, eqs 6 and 7). Starting with the products of the coupling reaction, syntheses of the prostaglandin intermediates 13 and 14 (for 11-deoxy-PGE2 and PGA2) and Δ7-PGA1 methyl ester (15) were accomplished efficiently. During these investigations, LDA, LiCA, and LHMDS were found to be equally efficient bases for aldol reaction at the α′ (α prime) position of cyclopentenones 39, 40, and 41 (Table 3).

Regio- and stereoselective installation of alkyl groups onto cis 4-cyclopentene-1,3-diol monoacetate by using reagents derived from alkylmagnesium halides

Reaction of cis 4-cyclopentene-1,3-diol monoacetate with alkyl reagents derived from RMgX and CuCN furnished either trans 4-alkyl-2-cyclopenten-1-ols (1,4-isomers) or trans 2-alkyl-3-cyclopenten-1-ols (1,2-isomers) depending upon the stoichiometry of RMgX

Realization of high regioselectivity in the coupling reaction of a cyclopentadiene monoepoxide equivalent and aryl nucleophiles

Coupling reaction of monoacetate 2 and aryl hard nucleophiles is realized for the first time, which consists of the lithium arylborates as hard nucleophiles and NiCl2(PPh3)2 as a catalyst. More importantly, the independent effects of t-BuCN and NaI and their synergistic function are discovered to increase regioselectivity furnishing trans 1,3-isomers 6 as the major products.