414869-14-0Relevant articles and documents
A catalytic and enantioselective desymmetrization of meso cyclic allylic bisdiethylphosphates with organozinc reagents
Piarulli, Umberto,Daubos, Philippe,Claverie, Christelle,Roux, Maryline,Gennari, Cesare
, p. 234 - 236 (2003)
The chosen one: The desymmetrization of meso-2 is possible with the use of diethylzinc in the presence of the Cu' complex of 1 (10 mol%; Tf = CF3SO2). Ligand 1 was optimized from a screen of a library of 125 compounds. Other ligands
Addition of organozinc species to cyclic 1,3-diene monoepoxide
Xue, Song,Li, Yali,Han, Kaizhen,Yin, Wen,Wang, Meng,Guo, Qingxiang
, p. 905 - 907 (2002)
(equation presented) The reaction of organozinc reagents (ZnEt2, ZnPh2) with cyclic 1,3-diene monoepoxides in the presence of CF3COOH gave the cis-addition products. Lewis acids such as (CF3CO2)2
Copper-catalyzed γ-selective and stereospecific allyl-aryl coupling between (Z)-acyclic and cyclic allylic phosphates and arylboronates
Ohmiya, Hirohisa,Yokokawa, Natsumi,Sawamura, Masaya
supporting information; experimental part, p. 2438 - 2440 (2010/07/10)
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.
Palladium-catalyzed γ-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids
Ohmiya, Hirohisa,Makida, Yusuke,Li, Dong,Tanabe, Masahito,Sawamura, Masaya
supporting information; experimental part, p. 879 - 889 (2010/03/25)
Reactions between acyclic (E)-allylic acetates and arylboronic acids in the presence of a palladium catalyst prepared from Pd(OAc)2, phenanthroline (or bipyridine), and AgSbF6 (1:1.2:1) proceeded with excellent γ-selectivity to afford allyl-aryl coupling products with E-configuration. The reactions of α-chiral allylic acetates took place with excellent α-to-γ chirality transfer with syn stereochemistry to give allylated arenes with a stereogenic center at the benzylic position. The reaction tolerated a broad range of functional groups in both the allylic acetates and the arylboronic acids. Furthermore, γ-arylation of cinnamyl alcohol derivatives afforded gem-diarylalkane derivatives containing an unconjugated alkenic substituent. The synthetic utility of this method was demonstrated by its utilization in an efficient synthesis of (+)-sertraline, an antidepressant agent. The observed γ-regioselectivity and E-1,3-syn stereochemistry were rationalized based on a Pd(II) mechanism involving transmetalation between a cationic mono(acyloxo)palladium(II) complex and arylboronic acid, and directed carbopalladation followed by syn-β-acyloxy elimination. The results of stoichiometric reactions of palladium complexes related to possible intermediates were fully consistent with the proposed mechanism.
Ligand-controlled selectivity in the desymmetrization of meso cyclopenten-1,4-diols via rhodium(I)-Catalyzed addition of arylboronic acids
Menard, Frederic,Perez, David,Sustac Roman, Daniela,Chapman, Timothy M.,Lautens, Mark
supporting information; experimental part, p. 4056 - 4068 (2010/08/07)
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.
Realization of anti-SN2′ selective allylation of 4-cyclopentene-1,3-diol monoester with aryl- and alkenyl-zinc reagents
Nakata, Kenya,Kiyotsuka, Yohei,Kitazume, Tomoya,Kobayashi, Yuichi
body text, p. 1345 - 1348 (2009/05/07)
(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
Miura, Tomoya,Takahashi, Yusuke,Murakami, Masahiro
, p. 595 - 597 (2007/10/03)
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
Rhodium-catalyzed asymmetric allylic substitution with boronic acid nucleophiles
Menard, Frederic,Chapman, Timothy M.,Dockendorff, Chris,Lautens, Mark
, p. 4569 - 4572 (2007/10/03)
An enantio-, regio-, and diastereoselective rhodium(I)-catalyzed desymmetrization of a meso-cyclic allylic dicarbonate with organoboronic acid nucleophiles is described. The rhodium(I) catalyst formed in situ from [Rh(cod)OH]2 and Xyl-P-PHOS al
Aryl- and alkenyllithium preparations and copper-catalyzed reaction between the derived magnesium reagents and the monoacetate of 4-cyclopentene-1,3-diol
Nakata, Kenya,Kobayashi, Yuichi
, p. 1319 - 1322 (2007/10/03)
(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
New reagent system for attaining high regio- and stereoselectivities in allylic displacement of 4-cyclopentene-1,3-diol monoacetate with aryl- and alkenylmagnesium bromides
Kobayashi, Yuichi,Nakata, Kenya,Ainai, Takayuki
, p. 183 - 186 (2007/10/03)
(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
