83494-26-2Relevant academic research and scientific papers
Multisubstituted pyrazole synthesis via [3?+?2] cycloaddition/rearrangement/N[sbnd]H insertion cascade reaction of α-diazoesters and ynones
Feng, Xiaoming,Liu, Xiaohua,Zeng, Zi,Zhao, Peng
supporting information, p. 132 - 135 (2020/12/21)
The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)3 as the catalyst are described. A series of 4-substituted pyrazoles were obtained via [3 + 2] cycloaddition, 1,5-ester shift, 1,3-H shift, and N[sbnd]H insertion process. Deuterium labelling experiments, kinetic studies and control experiments were carried out for the rationalization of the mechanism.
A bifunctional ligand enables efficient gold-catalyzed hydroarylation of terminal unactivated propargylic alcohols with heteroareneboronic acids
Liao, Shengrong,Xu, Huayan,Xu, Liang,Liang, Baoxia,Yang, Bin,Wang, Junfeng,Zhou, Xuefeng,Lin, Xiuping,Luo, Zaigang,Liu, Yonghong
, (2020/11/27)
Terminal allylic alcohols are important motifs in natural products, and also key intermediates/precursors in numerous novel reaction transformations. In this study, enabled by a bifunctional ligand featuring a basic amino group, a gold-catalyzed hydroarylation of terminal unactivated propargylic alcohols with heteroareneboronic acids has been first established, and efficiently affords various terminal aryl-substituted allylic alcohols with moderate to high yields under mild conditions.
Synthesis of (Z)-alkene-containing linear conjugated dienyl homoallylic alcohols by a palladium-catalyzed three-component reaction
Horino, Yoshikazu,Sakamoto, Juri,Murakami, Miki,Sugata, Miki
supporting information, p. 1323 - 1327 (2020/08/21)
A synthesis of (Z)-alkene-containing linear conjugated dienyl homoallylic alcohols by using a palladium-catalyzed three-component reaction has been developed. This method shows good functional-group compatibility and generality, with high diastereoselectivity. Additionally, in many cases, the present method controls the alkene stereochemistry of the newly formed C-C bond and overcomes the inherent preference for (E)-alkene formation, giving (Z, E)- and (Z, Z)-products.
Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross-Linking
Du Prez, Filip E.,Guerre, Marc,Maes, Diederick,Unal, Kamil,Van Herck, Niels,Winne, Johan M.
supporting information, p. 3609 - 3617 (2020/02/04)
The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross-linkers for thiols. The click-like thiol–yne cross-linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross-linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne-based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross-linker.
Trialkylborane-Mediated Multicomponent Reaction for the Diastereoselective Synthesis of Anti-δ,δ-Disubstituted Homoallylic Alcohols
Horino, Yoshikazu,Murakami, Miki,Aimono, Ataru,Lee, Jun Hee,Abe, Hitoshi
supporting information, p. 476 - 480 (2019/01/14)
The trialkylborane/O2-mediated reaction of propargyl acetates having a tributylstannyl group at an alkyne terminus with aldehydes in a THF-H2O solvent system gave anti-δ,δ-disubstituted homoallylic alcohols with good to high diastereoselectivity. Intriguingly, two alkyl groups derived from trialkylborane were embedded into the reaction product. The trialkylborane plays a key role not only as a radical initiator but also as a source of alkyl radicals.
Phosphorous acid promoted isomerization of propargyl alcohols to α,β-unsaturated carbonyl compounds
Gan, Xiaotang,Fu, Zuqi,Liu,Yan, Yani,Chen, Chao,Zhou, Yongbo,Dong, Jianyu
supporting information, (2019/07/12)
A metal-free and two-phase protocol for the Meyer-Schuster isomerization of propargyl alcohols to the corresponding α,β-unsaturated carbonyl compounds has been achieved in the presence of stoichiometric phosphorous acid aqueous solution, which produces the desired products in high yields with excellent stereoselectivity. Compared with the traditional methods, the procedure features broad scope of the substrates, mild conditions, and easy separation, providing an appealing alternative to the Meyer-Schuster reaction.
Gem-Digold Acetylide Complexes for Catalytic Intermolecular [4 + 2] Cycloaddition: Having Two Gold Centers Is Better for Asymmetric Catalysis
Nanko, Masaki,Shibuya, Satoru,Inaba, Yuya,Ono, Soichiro,Ito, Shigekazu,Mikami, Koichi
supporting information, p. 7353 - 7357 (2018/10/15)
Gold(I)-catalyzed highly enantioselective intermolecular [4 + 2] cycloaddition is shown with ynones and cyclohexadiene. Various bicyclo[2.2.2]octadiene derivatives are produced in high yields (up to 99%) with good enantioselectivity (up to 96% ee). Key to the success is generation of the gem-digold terminal alkyne as a catalytic on-cycle species. As proof of the gem-digold catalysis, a positive nonlinear effect is clarified between the ee's of the ligand and the cycloadduct.
Styrene as 4π-Component in Zn(II)-Catalyzed Intermolecular Diels-Alder/Ene Tandem Reaction
Zheng, Min,Wu, Feng,Chen, Kai,Zhu, Shifa
supporting information, p. 3554 - 3557 (2016/08/16)
A mild Zn-catalyzed intermolecular Diels-Alder/ene tandem reaction with styrene as a 4π-component is reported. A variety of dihydronaphthalene products could be prepared in moderate to good yields. Moreover, a combination of DFT calculations and experiments was performed to further understand the mechanism of this unique tandem reaction.
Trialkyl Methanetricarboxylate as Dialkyl Malonate Surrogate in Copper-Catalyzed Enantioselective Propargylic Substitution
Huang, Guanxin,Cheng, Cang,Ge, Luo,Guo, Beibei,Zhao, Long,Wu, Xiaoyu
supporting information, p. 4894 - 4897 (2015/10/12)
The first copper-catalyzed enantioselective propargylation of trialkyl methantricarboxylate with propargylic alcohol derivatives was developed. The tricarboxylate unit in the obtained adducts could be easily transformed into a malonate moiety by treating with in situ generated NaOEt in excellent yield without racemization.
Diastereo- and enantioselective propargylation of benzofuranones catalyzed by pybox-copper complex
Zhao, Long,Huang, Guanxin,Guo, Beibei,Xu, Lijun,Chen, Jie,Cao, Weiguo,Zhao, Gang,Wu, Xiaoyu
supporting information, p. 5584 - 5587 (2015/02/19)
Diastereo- and enantioselective preparation of 2,2-disubstituted benzofuran-3(2H)-one has been realized by a pybox-copper catalyzed reaction between 2-substituted benzofuran-3(2H)-one and propargyl acetate. The utility of this method was demonstrated by further transformation of the terminal alkyne into a methyl ketone without loss of enantiomeric purity.
