150805-64-4Relevant articles and documents
Me2s-induced highly selective reduction of aldehydes in the presence of ketones involving aldehyde-selective rate enhancement: A triruthenium cluster-catalyzed hydrosilylation
Yumino, Shohei,Hashimoto, Toru,Tahara, Atsushi,Nagashima, Hideo
, p. 1829 - 1831 (2014)
Addition of appropriate amounts of Me2S unusually accelerated the hydrosilylation of aldehydes catalyzed by [Ru3(CO)7(Acy)] (1, Acy: μ3-η2,η3,η5-acenaphthylene). The reduction of
Binuclear Pd(I)-Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes
Zhang, Yang,Torker, Sebastian,Sigrist, Michel,Bregovi?, Nikola,Dydio, Pawe?
supporting information, p. 18251 - 18265 (2020/11/02)
Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>107 metric ton yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Here, we report a highly selective and exceptionally active catalyst system that is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader context, the new mechanistic understanding enables the development of other carbonylation reactions of high importance to chemical industry.
Enantioselective Iridium-Catalyzed Allylation of Acetylenic Ketones via 2-Propanol-Mediated Reductive Coupling of Allyl Acetate: C14-C23 of Pladienolide D
Brito, Gilmar A.,Jung, Woo-Ok,Yoo, Minjin,Krische, Michael J.
supporting information, p. 18803 - 18807 (2019/11/19)
Highly enantioselective catalytic reductive coupling of allyl acetate with acetylenic ketones occurs in a chemoselective manner in the presence of aliphatic or aromatic ketones. This method was used to construct C14-C23 of pladienolide D in half the steps previously required.
Heck arylation of allyl alcohol catalyzed by Pd(0) nanoparticles
Tarnowicz, Stanis?awa,Alsalahi, Waleed,Mieczyńska, Ewa,Trzeciak, Anna M.
, p. 5605 - 5612 (2017/08/26)
Pd(0) nanoparticles ca. 2 nm in diameter were obtained by the reduction of PdCl2 and Pd(OAc)2 in water at 80 °C in the presence of a PVP-stabilizing polymer. Pd(0) NPs were successfully used in the Heck coupling of allyl alcohol with iodo- and bromobenzenes. Iodobenzenes reacted under solventless conditions or in DMF solution producing 3-arylpropanals and 2-arylpropanals as the main products. The same products were obtained in the reaction of bromobenzene in TBAB as the reaction medium. The stability of Pd(0) NPs was evidenced in recycling experiments. Similar Heck coupling results were also obtained with the palladium compounds PdCl2(cod) and Pd(OAc)2 under the same conditions.
Replacing a stoichiometric silver oxidant with air: Ligated Pd(II)-catalysis to β-aryl carbonyl derivatives with improved chemoselectivity
Vellakkaran, Mari,Andappan, Murugaiah M.S.,Kommu, Nagaiah
supporting information, p. 2788 - 2797 (2014/05/06)
Air was employed as a green reoxidant of Pd(0), replacing stoichiometric and toxic silver salt, in the chelation-controlled Pd(II)-modulated arylative enolization of prop-2-en-1-ols to acquire synthetically-important β-aryl carbonyl derivatives. This green approach, which didn't require acid or base, allowed the compatibility of a range of functionalities (inclusive of -I, -Br & -Cl), resulting in the construction of structurally-diverse dihydrochalcones, α-benzyl-α′-alkyl acetones, α-benzyl β-keto esters and dihydrocinnamaldehydes. In addition to organoboronic acids, efficient coupling was also achieved with boronic esters and trifluoroborate salts. A deuterium labelling experiment revealed an interesting 1,2-hydrogen shift after β-arylation in the catalytic process. the Partner Organisations 2014.
A novel consecutive three-component Heck-isomerization-Wittig sequence by way of in situ generated aldehydes
Panther, Jesco,Roehrich, Adalbert,Mueller, Thomas J. J.
, p. 297 - 311 (2013/09/24)
A novel consecutive three-component four step synthesis of 5-(hetero)arylpent-2-enoates has been disclosed. Various (hetero)aryl iodides can be coupled with allyl alcohol under Heck conditions to give 3-(hetero)arylpropionaldehyde intermediates, which were transformed without isolation with in situ generated stabilized phosphorus ylides to furnish 5-(hetero)arylpent-2-enoates in moderate to excellent yield. This one-pot procedure circumvents the isolation of sensitive aldehydes and phosphorus ylides as intermediates and finally gives the product isomers with good to excellent E/Z and β/α selectivity. ARKAT-USA, Inc.
Ligated regioselective PdII catalysis to access β-aryl-bearing aldehydes, ketones, and β-keto esters
Vellakkaran, Mari,Andappan, Murugaiah M. S.,Kommu, Nagaiah
supporting information; experimental part, p. 4694 - 4698 (2012/09/22)
By employing ligands in the PdII-mediated arylative isomerization of allyl alcohols, a milder and regioselective access to the versatile building blocks β-aryl aldehydes and ketones was developed. This new and chelation-controlled protocol enabled the compatibility of wide range of functionalities to generate dihydrochalcones, α-benzyl-α′- alkyl acetones, dihydrocinnamaldehydes, and α-benzyl β-keto esters (from Baylis-Hillman adducts). A practical multigram synthesis of an intermediate for Propafenone was also demonstrated. Copyright
Double arylation of allyl alcohol via a one-pot heck arylation- isomerization-acylation cascade
Colbon, Paul,Ruan, Jiwu,Purdie, Mark,Mulholland, Keith,Xiao, Jianliang
supporting information; experimental part, p. 5456 - 5459 (2011/12/05)
A one-pot, two-step catalytic protocol has been developed. A regioselective Heck coupling between aryl bromides and allyl alcohol leads to the generation of arylated allyl alcohols that in situ isomerize to give aldehydes, which then undergo an acylation reaction with a second aryl bromide. A variety of aryl bromides can be employed in both the initial Heck reaction and the acylation, providing easy access to a wide variety of substituted dihydrochalcones.
One-pot synthesis of symmetrical 1,3-diarylureas or substituted benzamides directly from benzylic primary alcohols and effective oxidation of secondary alcohols to ketones using phenyliodine diacetate in combination with sodium azide
Li, Xiao-Qiang,Wang, Wei-Kun,Han, Yi-Xin,Zhang, Chi
experimental part, p. 2588 - 2598 (2010/12/25)
Benzylic primary alcohols can be directly converted into symmetrical 1,3-diarylureas or substituted benzamides via an one-pot oxidative reaction using the combined reagent of phenyliodine diacetate and sodium azide. This new reaction constitutes a step-economical way to prepare symmetric 1,3-diarylureas or substituted benzamides depending upon the substituents on the phenyl rings of starting alcohols. The sodium acetate generated in situ from the ligand exchange between phenyliodine diacetate and sodium azide plays the pivotal role in the formation of 1,3-diarylureas. In addition, it is also found that various secondary alcohols can be readily oxidized to their corresponding ketones in excellent yields using the same reagent system of phenyliodine diacetate and sodium azide. Generally, secondary alcohols are preferentially oxidized to the corresponding ketones in the presence of primary ones with the limited amounts of phenyliodine diacetate and sodium azide.
METHOD FOR HYDROGENATION OF α,β-UNSATURATED CARBONYL COMPOUNDS
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Page/Page column 11, (2008/06/13)
A method for the chemoselective hydrogenation of a,? unsaturated carbonyl compounds is disclosed, in which compounds of general formula (I), where R1 = H, branched, unbranched, saturated or unsaturated 1-30C hydrocarbon group which may have suitable substituents and the hydrocarbon group may have one or more heteroatoms in the chain, aryl or heteroaryl group which can have suitable substituents, R2, R3 and R4 independently = H, F, Cl, Br, I, OH, CN, NO2, NO, SO2, SO3, amino, mono- and di-(C1-C24) alkyl substituted amino, mono- and di-(C5-C20) aryl substituted amino, imino, phosphono, phosphonato, phosphinato, phospho, phosphino, a branched, unbranched, saturated or unsaturated 1-30C hydrocarbon group which may have suitable substituents and the hydrocarbon group may have one or more heteroatoms in the chain, aryl or heteroaryl group which can have suitable substituents, each of R2, R3 and R4 can form a 5- or 6-membered ring or annelated 5-and/or 6-membered rings which can be aromatic, alicyclic, heteroaromatic or heteroalicyclic and have up to 4 substituents, are reacted with a hybrid donor to form a compound of general formula (II) in which R1, R2, R3 and R4 are as above. Said method permits the selective hydrogenation of a,? unsaturated aldehydes and ketones without the use of metal catalysts.
