69371-59-1Relevant academic research and scientific papers
Synthesis of Cyclic β-Silylalkenyl Triflates via an Alkenyl Cation Intermediate
Lee, Craig J.,Swain, Manisha,Kwon, Ohyun
, p. 5474 - 5477 (2018/09/13)
Trimethylsilylalkyne derivatives are transformed into cyclic β-silylalkenyl triflates through cationic cyclization and subsequent trapping of the alkenyl cation by a triflate anion. β-Silylcyclohexenyl triflates and 3-trimethylsilyl-1,4-dihydronaphth-2-yl
A New Route to Phenols: Palladium-Catalyzed Cyclization and Oxidation of γ,δ-Unsaturated Ketones
Samadi, Sadaf,Orellana, Arturo
, p. 2472 - 2475 (2016/08/25)
We report a new strategy for the synthesis of phenols from acyclic unsaturated ketones in one pot. The reaction proceeds by palladium-catalyzed carbopalladation of an alkene with the enol form of the tethered ketone, generating a substituted cyclohexanone. Upon introduction of a terminal oxidant a palladium-catalyzed oxidation ensues to give the desired phenol. This approach allows the programming of phenol substituents on the acyclic substrate and therefore circumvents the limitations inherent in traditional syntheses of phenols.
Cooperative Palladium/Proline-Catalyzed Direct α-Allylic Alkylation of Ketones with Alkynes
Yang, Chi,Zhang, Kaifan,Wu, Zijun,Yao, Hequan,Lin, Aijun
supporting information, p. 5332 - 5335 (2016/11/02)
The cooperative palladium/l-proline-catalyzed direct α-allylic alkylation of ketones with alkynes is achieved. This reaction exhibits high atom economy since a leaving group is not liberated and a stoichiometric amount of extra oxidant is not needed. A br
Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: Efficient access to α-alkyl vinylarenes
Zheng, Changwu,Stahl, Shannon S.
supporting information, p. 12771 - 12774 (2015/08/18)
Branched-selective oxidative Heck coupling reactions have been developed between arylboronic acids and electronically unbiased terminal alkenes. The reactions exhibit high catalyst-controlled regioselectivity favoring the less common branched isomer. The reactions employ a catalyst composed of Pd(TFA)2/dmphen (TFA = trifluoroacetate, dmphen = 2,9-dimethyl-1,10-phenanthroline) and proceed efficiently at 45-60 °C under 1 atm of O2 without requiring other additives. A broad array of functional groups, including aryl halide, allyl silane and carboxylic acids are tolerated.
Pd(0)-catalyzed 1,1-diarylation of ethylene and allylic carbonates
Saini, Vaneet,Liao, Longyan,Wang, Qiaofeng,Jana, Ranjan,Sigman, Matthew S.
supporting information, p. 5008 - 5011 (2013/10/22)
An efficient protocol for the one-step synthesis of biologically relevant 1,1-diarylalkanes has been described. This reaction introduces two different aryl groups across the terminal end of simple feedstock alkenes such as ethylene and allylic carbonates.
Lewis acid/CpRu dual catalysis in the enantioselective decarboxylative allylation of ketone enolates
Linder, David,Austeri, Martina,Lacour, Jerome
scheme or table, p. 4057 - 4061 (2009/12/06)
The addition of a Lewis acidic metal triflate salt Mg(OTf)2 as co-catalyst in the CpRu-catalyzed decarboxylative allylation of in situ-generated ketone enolates allows the reaction to proceed at lower temperature with higher regio- and enantios
Dual palladium-and proline-catalyzed allylic alkylation of enolizable ketones and aldehydes with allylic alcohols
Usui, Ippei,Schmidt, Stefan,Breit, Bernhard
supporting information; experimental part, p. 1453 - 1456 (2009/09/30)
The dual Pd/proline-catalyzed α-allylation reaction of a variety of enolizable ketones and aldehydes with allylic alcohols is described. In this reaction, the choice of a large-bite angle ligand Xantphos and proline as the organocatalyst was essential for generation of the crucial π-allyl Pd intermediate from allylic alcohol, followed by nucleophilic attack of the enamine formed in situ from the corresponding enolizable carbonyl substrate and proline.
Preparation of bicyclic 1,2,4-trioxanes from γ,δ-unsaturated ketones
Ramirez, Armando P.,Thomas, Andrew M.,Woerpel
supporting information; experimental part, p. 507 - 510 (2009/08/07)
(Chemical Equation Presented) Treatment of γ,δ-unsaturated ketones with hydrogen peroxide and acid provides a rapid entry into the medicinally important 1,2,4-trioxane structure. Alkene substitution that stabilizes carbocationic intermediates proved to be important for the success of this transformation.
Enantioselective CpRu-catalyzed carroll rearrangement - Ligand and metal source importance
Linder, David,Buron, Frederic,Constant, Samuel,Lacour, Jerome
supporting information; scheme or table, p. 5778 - 5785 (2009/06/18)
The addition of unstabilized carbonyl nucleophiles to unsymmetrical allyl-metal fragments still represents a challenge to generate stereogenic centers enantio- and regioselectively. In this context, the decarboxylative Carroll rearrangement of allyl β-keto esters is particularly interesting, since chiral γ,δ-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, with selected enantio-pure pyridine-monooxazoline ligands, catalyze this transformation and afford complete conversions along with good levels of regioselectivity and enantioselectivity. Even more challenging (electron-poor) substrates react (up to 86% ee, branched/linear ratio ≥ 97:03). In addition, the use of an air-stable metal precursor, namely [CpRu(η6-naphthalene)][PF6], allows the reaction to be carried out reproducibly even in non-anhydrous THF with a catalyst loading as low as 2 mol-%. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Sequenced Reactions with Samarium(II) Iodide. Domino Epoxide Ring-Opening/Ketyl Olefin Coupling Reactions
Molander, Gary A.,Losada, Carlos Del Pozo
, p. 2935 - 2943 (2007/10/03)
A new sequential reductive coupling process promoted by samarium(II) iodide is described. Cascade epoxide ring opening and ketyl radical olefin cyclization leads to a variety of cis-1,3-cyclopentanediols and cis-1,3-cyclohexanediols in good yields and with high diastereoselectivity.
