3‐Isothiocyanato Oxindoles Serving as Powerful and Versatile Precursors to Structurally Diverse Dispirocyclic Thiopyrrolidineoxindoles through a Cascade Michael/Cyclization Process with Amino‐Thiocarbamate Catalysts

Han, Wen‐Yong; Li, Shiwu; Wu, Zhijun; Zhang, Xiaomei; Yuan, Wei‐Cheng

doi:10.1002/chem.201300206

Cited by 105 publications

(12 citation statements)

References 72 publications

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“…For example, Yuan and co‐workers developed an asymmetric domino Michael addition/cyclization reaction of 409 and methyleneindolinones 587 . By using a chiral quinine‐derived thiocarbamate catalyst 588 , the bispirooxindole derivatives 586a were obtained in excellent yields and stereoselectivities (Scheme ) . On the other hand, Chen, Xiao, and co‐workers used a chiral quinine‐derived squaramide 448 as the catalyst to catalyze the same domino reactions between 409 and 587 and obtained the diastereomeric bispirooxindole derivatives 586b in excellent yields and stereoselectivities (Scheme )…”

Section: Multifunctional Catalystsmentioning

confidence: 99%

Recent Progress in Organocatalytic Asymmetric Domino Transformations

2017

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Sustainability in chemical synthesis is a major aspect of the current synthetic endeavors and, therefore,m imicking the biological process in the laboratory nowadays has the highest priority.T owards achieving this goal, designingorganic reactions in domino mode rathert han the multistep synthetic pathways andu sing organocatalysisi nstead of metal catalysis have received al ot of attention due to the inherenta dvantageso ft hese processes in terms of synthetic efficiencya nd sustainability.A saresult, the field of asymmetric organocatalytic domino reactions has witnessed tremendous progress in recent years.T his review attempts to summarize the latest developments in asymmetric organocatalyzed domino reactions since 2012, with the emphasis on the catalysts andr eactionm odes.D iscussions on the reactionm echanismsa nd the applications of the developed domino reactionm ethodsi nt he synthesis of biologically active molecules and natural products are also includedwhen appropriate.

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Section: Multifunctional Catalystsmentioning

confidence: 99%

Recent Progress in Organocatalytic Asymmetric Domino Transformations

2017

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“…Despite ample room for improvement, this sequence constitutes a new strategy for the synthesis of bis(spirooxindoles), which are privileged scaffolds with very limited synthetic methods known for their preparation. [26] In conclusion, we have developed a rare example of asymmetric triple relay catalysis through the sequential use of…”

Section: Methodsmentioning

confidence: 99%

Asymmetric Triple Relay Catalysis: Enantioselective Synthesis of Spirocyclic Indolines through a One‐Pot Process Featuring an Asymmetric 6π Electrocyclization

et al. 2014

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A rare example of a one-pot process that involves asymmetric triple relay catalysis is reported. The key step is an asymmetric [1,5] electrocyclic reaction of functionalized ketimines. The substrates for this process were obtained in situ in a two-step process that involved the hydrogenation of nitroarenes with a Pd/C catalyst to yield aryl amines and their subsequent coupling with isatin derivatives in a Brønsted acid catalyzed ketimine formation reaction. The electrocyclization was catalyzed by a bifunctional chiral Brønsted base/ hydrogen bond donor catalyst. The one-pot process gave the desired products in good yields and with excellent enantioselectivity.Inspired by the multienzymatic tandem catalytic processes that nature uses for the efficient synthesis of complex molecules, the development of multi-catalyst-promoted asymmetric tandem reactions (MPATR) is of current interest. [1] Aside from the general advantages of tandem catalysis, [2] namely the effectiveness in minimizing waste production, the consumption of energy, labor, and time, and yield losses associated with the purification of intermediates, the use of multiple catalysts, rather than a single catalyst, offers the promise to incorporate more substrates and reaction types to design novel cascade reactions, which are very attractive for building up molecular complexity from simple materials. [1] Over the past decade, much progress has been made in this area, and asymmetric relay catalysis (or sequential catalysis) has been established as a major type of MPATR, [1, 3] which refers to the sequential combination of catalytic reactions, each of which is independently operated by a distinct catalyst, into a one-pot process. Nevertheless, despite remarkable advances in the development of tandem reactions that were achieved by using two metal catalysts, [4] two organocatalysts, [5] or a metal and an organocatalyst, [6] the combination of three distinct catalysts to exploit asymmetric triple relay catalysis is still underdeveloped, although it has already exhibited its powerfulness in tackling some synthetic challenges. [7] On the other hand, the ever-increasing demand in chemical biology and medicinal research for synthetic libraries derived from privileged scaffolds requires the development of new synthetic methods that enable the construction of libraries of optically active compounds with polycyclic structures. [8] In particular, efficient stereoselective syntheses of spirocyclic compounds are very much in demand. [9] Therefore, the exploration of asymmetric triple relay catalysis for the facile construction of spirocyclic compounds from simple materials is highly desirable. Herein, we report an unprecedented example of asymmetric triple replay catalysis, which integrates palladium, Brønsted acid, and bifunctional chiral Brønsted base/hydrogen bond donor catalysis, and we demonstrate its effectiveness in the highly enantioselective synthesis of oxindole-based spirocyclic indolines through a onepot sequence that involves hydrogenation, ketimine format...

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“…The following examples illustrate the progress in this area. In 2013, an efficient asymmetric cascade Michael/cyclization reaction of 3-isothiocyanato oxindoles (2) with alkylidene azlactones (43) or 3-methylene-2-oxindoles (35) to construct more complex dispirocyclic thiopyrrolidineoxindoles was explored by our group [32], providing a range of highly functionalized dispirocyclooxindole compounds (44 and 45a) in excellent results (up to 99% yield, >99:1 dr, and >99% ee) only using 1 mol% of readily available aminothiocarbamate catalyst (8m) (Scheme 15).…”

Section: Recent Advances In Organocatalysismentioning

confidence: 99%

“…Encouraged by our these progresses using 3-isothiocyanato oxindoles (2) as powerful and versatile precursors in the organocatalytic asymmetric cascade Michael/cyclization reactions [32,33], we further attempted to investigate the reactions of 3-isothiocyanato oxindoles (2) with unsaturated isoxazolones (48) and pyrazolones (40) (Scheme 15) [34]. It was observed that the reaction also worked well with quinine as catalyst under mild reaction conditions, delivering two kinds of spirooxindole derivatives (49 and 50) in high to excellent yields with moderate to good stereoselectivities.…”

Section: Recent Advances In Organocatalysismentioning

confidence: 99%