479213-83-7Relevant academic research and scientific papers
Enantioselective alkynylations of aromatic and aliphatic aldehydes catalyzed by terpene derived chiral amino alcohols
Watts, Cian Christopher,Thoniyot, Praveen,Hirayama, Lacie C.,Romano, Talia,Singaram, Bakthan
, p. 1829 - 1835 (2005)
Enantioselective alkynyl zinc additions to aromatic and aliphatic aldehydes have been studied using terpene derived chiral amino alcohol ligands. The limonene derived amino alcohol (1R,2R,5S)-2-methyl-5-(1-methylethenyl)-2-(1- pyrrolidinyl)cyclohexanol ga
Visible Light-Induced Reductive Alkynylation of Aldehydes by Umpolung Approach
Tanaka, Ibuki,Sawamura, Masaya,Shimizu, Yohei
supporting information, p. 520 - 524 (2022/01/20)
Reductive alkynylation of aldehydes by the Umpolung approach was developed using a photoredox catalyst under blue LED irradiation. Ketyl radicals, generated by single-electron reduction of aldehydes through proton-coupled electron transfer (PCET), reacted with electrophilic alkynylsulfones. Sterically demanding bulky aldehydes reacted smoothly under the Umpolung reaction conditions. Moreover, the alkynylation proceeded chemoselectively with an aryl aldehyde group in the presence of other carbonyl groups including an aliphatic aldehyde group.
DBU-Catalyzed Rearrangement of Secondary Propargylic Alcohols: An Efficient and Cost-Effective Route to Chalcone Derivatives
De, Rimpa,Savarimuthu, Antony,Ballav, Tamal,Singh, Pijush,Nanda, Jayanta,Hasija, Avantika,Chopra, Deepak,Bera, Mrinal K.
supporting information, p. 1587 - 1592 (2020/08/28)
A 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-catalyzed rearrangement of diarylated secondary propargylic alcohols to give α,β-unsaturated carbonyl compounds has been developed. The typical 1,3-transposition of oxy functionality, characteristic of Mayer-Schuster rearrangements, is not observed in this case. A broad substrate scope, functional-group tolerance, operational simplicity, complete atom economy, and excellent yields are among the prominent features of the reaction. Additionally, the photophysical properties and crystal-structure-packing behavior of selected compounds were investigated and found to be of interest.
Combining Electronic and Steric Effects to Generate Hindered Propargylic Alcohols in High Enantiomeric Excess
Vyas, Vijyesh K.,Knighton, Richard C.,Bhanage, Bhalchandra M.,Wills, Martin
supporting information, p. 975 - 978 (2018/02/23)
Tethered ruthenium-TsDPEN complexes have been applied to the catalysis of the asymmetric transfer hydrogenation of a range of aryl/acetylenic ketones. The introduction of an ortho- substituent to the aryl ring of the substrate results in a reversal of the
Alkynylation of aldehydes mediated by zinc and allyl bromide: a practical synthesis of propargylic alcohols
Zhou, Ji-Cai,Zhao, Lei,Li, Yuan,Fu, Ding-Qiang,Li, Zi-Cheng,Huang, Wen-Cai
, p. 4283 - 4294 (2017/06/20)
Abstract: A practical synthesis of propargylic alcohols was developed by alkynylation of aldehydes mediated by zinc and allyl bromide. Aromatic, aliphatic and vinyl aldehydes react with phenylacetylene or 1-hexyne to obtain various propargylic alcohols at room temperature in up to 98% yield. This method is characterized with inexpensive materials, wide substrate scope, and mild reaction conditions, and is also easy to scale up. In addition, this protocol is applicable to the alkynylation of α-ketone esters and epoxides to generate α-tertiary-hydroxy esters and α-alkynyl alcohols, respectively. Graphical Abstract: [Figure not available: see fulltext.].
Highly Efficient Synthesis of Multi-Substituted Allenes from Propargyl Acetates and Organoaluminum Reagents Mediated by Palladium
Zhang, Zhen,Shao, Xuebei,Zhang, Gang,Li, Qinghan,Li, Xinying
, p. 3643 - 3653 (2017/08/16)
A simple and mild catalytic S N 2′ substitution reaction of propargyl acetates with organoaluminum reagents is reported. The S N 2′ substitution reaction of propargyl acetates with organoaluminum reagents mediated by Pd(PhP 3) 2 Cl 2 (1 mol%)/PPh 3 (2 mol%)/K 2 CO 3 in tetrahydrofuran at 60 °C for 3-4 hours afforded the corresponding multi-substituted allenes in good yields (up to 94%) with high selectivities (up to 99%). The process was simple and easily performed, which offers an efficient method to synthesize the multi-substituted allene derivatives.
Enantioselective Alkynylation of Aromatic Aldehydes Catalyzed by a Sterically Highly Demanding Chiral-at-Rhodium Lewis Acid
Luo, Shipeng,Zhang, Xiao,Zheng, Yu,Harms, Klaus,Zhang, Lilu,Meggers, Eric
, p. 8995 - 9005 (2017/09/11)
The enantioselective catalytic alkynylation of aromatic aldehydes is reported using a sterically highly hindered bis-cyclometalated rhodium-based Lewis acid catalyst featuring the octahedral metal as the only stereogenic center. Yields of 58-98% with 79-9
Synthesis of 2-Sulfenylindenones via One-Pot Tandem Meyer-Schuster Rearrangement and Radical Cyclization of Arylpropynols with Disulfides
Zhang, Xing-Song,Jiao, Jun-Ying,Zhang, Xiao-Hong,Hu, Bo-Lun,Zhang, Xing-Guo
, p. 5710 - 5716 (2016/07/13)
A tandem annulation of arylpropynols with disulfides has been developed for the synthesis of 2-sulfenylindenone derivatives. The reaction pathway involves one-pot tandem Meyer-Schuster rearrangement of arylpropynols and successive radical cyclization with disulfides. Various arylpropynols and disulfides with a number of functional groups are compatible in this reaction that affords the corresponding 2-sulfenylindenones in moderate to good yields.
Base-mediated cascade rearrangements of aryl-substituted diallyl ethers
Reid, Jolene P.,McAdam, Catherine A.,Johnston, Adam J. S.,Grayson, Matthew N.,Goodman, Jonathan M.,Cook, Matthew J.
, p. 1472 - 1498 (2015/02/19)
Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig-oxy-Cope and isomerization-Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated that the role of the base and solvent was key to the reactivity and selectivity observed. Crossover experiments also suggest that these reactions proceed with a certain degree of dissociation, and the mechanistic pathway is highly complex with multiple competing routes.
A convenient approach to β-heteroarylated (C-N bond) ketones from Cs2CO3 promoted reaction between propargyl alcohols and nitrogen-heterocycles
Bhanuchandra,Kuram, Malleswara Rao,Sahoo, Akhila K.
experimental part, p. 3538 - 3555 (2012/05/20)
An efficient and direct approach to β-heteroarylated (C-N bond) ketones is demonstrated. Base promoted redox isomerization of propargyl alcohol to α,β-unsaturated ketone followed by conjugate addition to NH-heteroarenes affords a wide range of β-heteroarylated ketones in good to excellent yields. Aryl, heteroaryl, alkyl C(sp), and terminal alkynes containing unactivated propargyl alcohols effectively undergo redox-isomerization conjugate addition (RICA) with NH-heteroarenes. Reaction of 3-substituted pyrazoles or indazole with propargyl alcohols enables highly regioselective products. A diverse range of NH-bearing nucleophiles such as: pyrazoles, imidazole, triazoles, pyrrole, indoles and aniline participate in this reaction and deliver the corresponding β-heteroarylated ketones.
