2459-10-1Relevant articles and documents
Domino retro Diels-Alder/Diels-Alder reaction: An efficient protocol for the synthesis of highly functionalized bicyclo[2.2.2]octenones and bicyclo[2.2.2]octadienones
Chittimalla, Santhosh Kumar,Shiao, Hui-Yi,Liao, Chun-Chen
, p. 2267 - 2277 (2006)
A novel and convenient approach, the domino retro Diels-Alder/Diels-Alder reaction sequence for highly stereo- and regioselective synthesis of various bicyclo[2.2.2]octenone and bicyclo[2.2.2]octadienone derivatives is presented. Thus, the masked o-benzoquinones (MOBs) 2a-e generated by the pyrolysis of the respective dimers 3a-e participated in this novel synthetic strategy with a variety of olefinic and acetylenic dienophiles at 220 °C to provide the title compounds in good to excellent yields. The Royal Society of Chemistry 2006.
H-BPin/KOtBu Promoted Activation of Cobalt Salt to a Heterotopic Catalyst for Highly Selective Cyclotrimerization of Alkynes
Song, Shuo,Li, Chuhan,Liu, Tianfen,Zhang, Panke,Wang, Xiaoming
supporting information, p. 6925 - 6930 (2021/09/14)
A mixture of HBPin with KOtBu was found to activate cobalt salt to form a heterotopic cobalt species that is highly active for catalytic intermolecular trimerization of alkynes. This protocol affords 1,2,4-regioisomers in good yields with high regioselectivities under mild conditions. These salient features, together with the operational simplicity and high efficiency, as well as obviating the use of any costly and/or air sensitive ligands, renders the protocol promising for practical applications.
Sustainable synthesis of 1,2,3,4-cyclohexanetetracarboxylate from sugar-derived carboxylic acids
Jiang, Huifang,Lu, Fang,Lu, Rui,Luo, Xiaolin,Si, Xiaoqin,Xu, Jie
supporting information, p. 7499 - 7502 (2020/07/15)
Herein, we report a sustainable route for the synthesis of 1,2,3,4-cyclohexanetetracarboxylate from sugar-derived muconic acid and fumaric acid. The key Diels-Alder reaction constructed a cyclohexene framework substituted by four ester groups. The isolated yield of tetramethyl 5-cyclohexene-1,2,3,4-tetracarboxylate was up to 95.5percent without any catalyst used. And the hydrogenation reaction of the cycloadduct was catalyzed by commercial RANEY? Ni at room temperature and nearly 100percent yield of the cyclohexyl target products was obtained. This journal is
Enhanced Catalytic Activity of Nickel Complexes of an Adaptive Diphosphine-Benzophenone Ligand in Alkyne Cyclotrimerization
Orsino, Alessio F.,Gutiérrez Del Campo, Manuel,Lutz, Martin,Moret, Marc-Etienne
, p. 2458 - 2481 (2019/03/08)
Adaptive ligands, which can adapt their coordination mode to the electronic structure of various catalytic intermediates, offer the potential to develop improved homogeneous catalysts in terms of activity and selectivity. 2,2′-Diphosphinobenzophenones have previously been shown to act as adaptive ligands, the central ketone moiety preferentially coordinating reduced metal centers. Herein, the utility of this scaffold in nickel-catalyzed alkyne cyclotrimerization is investigated. The complex [(p-tolL1)Ni(BPI)] (p-tolL1 = 2,2′-bis(di(para-tolyl)phosphino)-benzophenone; BPI = benzophenone imine) is an active catalyst in the [2 + 2 + 2] cyclotrimerization of terminal alkynes, selectively affording 1,2,4-substituted benzenes from terminal alkynes. In particular, this catalyst outperforms closely related bi- and tridentate phosphine-based Ni catalysts. This suggests a reaction pathway involving a hemilabile interaction of the C-O unit with the nickel center. This is further borne out by a comparative study of the observed resting states and DFT calculations.
