4361-25-5Relevant academic research and scientific papers
Micelle-Mediated Trimerization of Ynals to Orthogonally Substituted 4H-Pyrans in Water: Downstream Rearrangement to Bioactive 2,8-dioxabicyclo[3.3.1]nona-3,6-diene Frameworks
Rashid, Showkat,Bhat, Bilal A.,Mehta, Goverdhan
supporting information, p. 6646 - 6651 (2021/10/14)
An efficient trimerization of ynals to diversely substituted 4H-pyran constructs has been executed in water, under ambient conditions employing micellar catalysis. The method is in agreement with the ideas of green and sustainable chemistry. The locus of the micellar reaction site has been probed through proton NMR studies. A general acid-mediated downstream rearrangement of the derived 4H-pyrans to interesting 2,8-dioxabicyclo[3.3.1]nona-3,6-dienes has been observed.
Rhodium-Catalyzed 1,1-Hydroacylation of Thioacyl Carbenes with Alkynyl Aldehydes and Subsequent Cyclization
Zhou, Bingnan,Wu, Qiuyue,Dong, Ziyang,Xu, Jiaxi,Yang, Zhanhui
supporting information, p. 3594 - 3599 (2019/05/24)
A rhodium-catalyzed 1,1-hydroacylation of thioacyl carbenes with alkynyl and alkenyl aldehydes and subsequent 6-endo-trig/dig cyclization are realized, giving structurally diverse 4H-thiopyran-4-ones and 2,3-dihydro-4H-thiopyran-4-ones in moderate to good yields. The oxidative addition of Rh(I) to aldehydes is proposed to be the turnover-limiting step. Manipulations of estrones demonstrate the applications of our formal (3 + 3) transannulations in the structural modifications of natural products.
Palladium-catalyzed oxidative borylation of conjugated enynones through carbene migratory insertion: synthesis of furyl-substituted alkenylboronates
Ping, Yifan,Chang, Taiwei,Wang, Kang,Huo, Jingfeng,Wang, Jianbo
supporting information, p. 59 - 62 (2019/01/03)
A palladium-catalyzed oxidative borylation reaction of conjugated enynones is developed. This reaction represents a new method for the synthesis of furyl-substituted alkenylboronates. The reaction works well with a series of conjugated enynones. Boryl migratory insertion of the palladium carbene intermediate is proposed as the key step in these transformations.
Copper-Catalyzed Asymmetric Silylation of Propargyl Dichlorides: Access to Enantioenriched Functionalized Allenylsilanes
Liu, Zheng-Li,Yang, Chao,Xue, Qi-Yan,Zhao, Meng,Shan, Cui-Cui,Xu, Yun-He,Loh, Teck-Peng
supporting information, p. 16538 - 16542 (2019/11/11)
A copper-catalyzed silylation of propargyl dichlorides was developed to access chloro-substituted allenylsilanes under mild reaction conditions. Moreover, enantioenriched chloro-substituted allenylsilanes can be synthesized in moderate to high yields and good enantioselectivities with this protocol.
Copper(II)-catalyzed silylation of activated alkynes in water: Diastereodivergent access to E- or Z-β-silyl-α,β-unsaturated carbonyl and carboxyl compounds
Calderone, Joseph A.,Santos, Webster L.
supporting information, p. 4154 - 4158 (2014/05/06)
Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was investigated. Through the activation of Me2PhSiBpin in water at room temperature and open atmosphere, vinylsilanes conjugated to carbonyl groups are synthesized in high yield. A surprising diastereodivergent access to olefin geometry was discovered using a silyl conjugate addition strategy: aldehydes and ketones were Z selective while esters and amides were exclusively transformed into the E products. Dial a diastereomer: The title reaction proceeds through the activation of Me2PhSiBpin in water at room temperature and open atmosphere to produce high yields of vinylsilanes conjugated to carbonyl groups. A surprising diastereodivergent access to olefin geometry was discovered using this silyl conjugate addition strategy: aldehydes were Z selective while esters and amides exclusively delivered the E-configured products.
Catalytic Asymmetric Synthesis of Alkynyl Aziridines: Both Enantiomers of cis-Aziridines from One Enantiomer of the Catalyst
Guan, Yong,L?pez-Alberca, Maria P.,Lu, Zhenjie,Zhang, Yu,Desai, Aman A.,Patwardhan, Aniruddha P.,Dai, Yijing,Vetticatt, Mathew J.,Wulff, William D.
supporting information, p. 13894 - 13900 (2016/02/18)
Alkynyl aziridines can be obtained from the catalytic asymmetric aziridination (AZ reaction) of alkynyl imines with diazo compounds in high yields and high asymmetric inductions mediated by a chiral boroxinate or BOROX catalyst. In contrast to the AZ reaction with aryl- and alkyl-substituted imines, alkynyl imines react to give cis-substituted aziridines with both diazo esters and diazo acetamides. Remarkably, however, the two diazo compounds give different enantiomers of the cis-aziridine from the same enantiomer of the catalyst. Theoretical considerations of the possible transition states for the enantiogenic step reveal that the switch in enantiomers results from a switch from Si-face to Re-face addition to the imine, which in turn is related to a switch from reaction with an E-imine in the former and a Z-isomer of the imine in the latter. The imine did it: The aziridination of alkynyl imines with diazo esters and diazo acetamides gives cis-aziridines with very high enantioselectivities. The absolute configuration of the cis-aziridine is reversed for the two diazo compounds even though the same enantiomer of the catalyst is used. The alkynyl imines can isomerize under the reaction conditions and the enantiomeric switch is proposed to result from the preferential reaction of E-imine with diazo esters and Z-imines with diazo acetamides.
Copper-Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers
Li, Hailing,Grassi, David,Guénée, Laure,Bürgi, Thomas,Alexakis, Alexandre
supporting information, p. 16694 - 16706 (2016/02/12)
An easy and versatile Cu-catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3-substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all-carbon quaternary stereogenic centers, through the copper-catalyzed enantiospecific 1,1/1,3-substitutions. The two successive copper-catalyzed reactions could be eventually combined into a one-pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses.
2-iodoxybenzenesulfonic acid as an extremely active catalyst for the selective oxidation of alcohols to aldehydes, ketones, carboxylic acids, and enones with oxone
Uyanik, Muhammet,Akakura, Matsujiro,Ishihara, Kazuaki
supporting information; experimental part, p. 251 - 262 (2009/06/28)
Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trad emark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5molpercentof 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16.
