One‐Pot Tandem Approach to Spirocyclic Oxindoles Featuring Adjacent Spiro‐Stereocenters

Liu, Yunling; Wang, Xin; Zhao, Yulei; Zhu, Feng; Zeng, Xing‐Ping; Chen, Long; Wang, Cuihong; Zhao, Xiao‐Li; Zhou, Jian

doi:10.1002/anie.201307250

Cited by 197 publications

(31 citation statements)

References 108 publications

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“…Furthermore, recent asymmetric [4+2], formal [3+3] and 1,3-dipolar cycloadditions developed by other research groups represent facile methods for the enantioselective construction of several versatile heterocyclic core structures (e.g., six-membered piperidine frameworks [15], 4-aminobenzopyrans [16], tetrahydrocarbazoles [17], 3-methylenepyrrolidines [18], hexahydrochromeno[4,3- b ]pyrrolidines [19], spirocyclic oxindole derivatives [20,21] and spiro[pyrazolidin-3,3′-oxindoles] [22]) widely present in numerous bioactive compounds and natural products.…”

Section: Cycloadditions Catalyzed By Chiral Binol-derived Phosphormentioning

confidence: 99%

Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances

2015

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Over the last several years there has been a huge increase in the development and applications of new efficient organocatalysts for enantioselective pericyclic reactions, which represent one of the most powerful types of organic transformations. Among these processes are cycloaddition reactions (e.g., [3+2]; formal [3+3]; [4+2]; vinylogous [4+2] and 1,3-dipolar cycloadditions), which belong to the most utilized reactions in organic synthesis of complex nitrogen-and oxygen-containing heterocyclic molecules. This review presents the breakthrough realized in this field using chiral BINOL-derived phosphoric acids and N-triflyl phosphoramide organocatalysts.

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Section: Cycloadditions Catalyzed By Chiral Binol-derived Phosphormentioning

confidence: 99%

Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances

2015

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“…[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 formation, and an asymmetric 6p electrocyclization (Scheme 1).As we are interested in the catalytic asymmetric synthesis of chiral spirocyclic compounds, [10] we wished to construct spirocyclic compounds through a [1,5] electrocyclic reaction of an imine as its catalytic asymmetric version is still in its infancy. [11] In 2009, the groups of List and Smith independ-Scheme 1.…”

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confidence: 99%

“…As we are interested in the catalytic asymmetric synthesis of chiral spirocyclic compounds, [10] we wished to construct spirocyclic compounds through a [1,5] electrocyclic reaction of an imine as its catalytic asymmetric version is still in its infancy. [11] In 2009, the groups of List and Smith independ-ently pioneered the catalytic asymmetric 6p electrocyclization.…”

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confidence: 99%

“…With our interests in oxindole chemistry, [10,16] we first designed isatin-derived malonate-ketimine 4 a as a starting point for the study of the asymmetric 6p electrocyclization, to pave the way for the subsequent development of the tandem reaction. It should be noted that whereas the catalytic asymmetric synthesis of spirocyclic oxindoles, a prominent structural motif in natural products, drugs, and bioactive products, [17] has been extensively studied, the asymmetric synthesis of spirocyclic oxindole-indoline derivatives is unprecedented.…”

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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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“…1a). Whereas syntheses of many classes of spirooxindole polycycles bearing Nheterocycles and spirooxindole all-carbon polycycles have been reported [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] , few examples of the syntheses of spirooxindole polycycles bearing O-heterocycles have been reported 22,23 . Most methods developed for the synthesis of the spirooxindole O-heterocycles provide nonpolycyclic derivatives [24][25][26][27][28][29][30][31][32][33] .…”

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Dynamic stereoselective annulation via aldol-oxa-cyclization cascade reaction to afford spirooxindole pyran polycycles

Sohail

Tanaka

2019

Commun Chem

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Spiro polycyclic compounds bearing pyran ring systems are found in bioactive molecules, and we recently reported the construction of spirooxindole all-carbon polycycles. Here we show the development of catalytic stereoselective annulation reactions that afford spirooxindole pyran polycycles. Oxindole-derived spiro[4,5]decanes are reacted with arylglyoxal to construct a pyran ring via the formation of carbon-carbon and carbon-oxygen bonds through dynamic aldol-oxa-cyclization cascade reactions, leading to the formation of spirooxindole pyran polycycles bearing six stereogenic centers as single diastereomers. During the reaction, the starting material is isomerized to the diastereomer, and this is key to afford the product. Taking advantage of this isomerization, highly enantiomerically enriched single diastereomers of spirooxindole pyran polycycles are obtained. The reactions generating the spiro pyran polycycles show stereoselectivities distinct from those previously observed in the construction of all-carbon polycycles.

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One‐Pot Tandem Approach to Spirocyclic Oxindoles Featuring Adjacent Spiro‐Stereocenters

Cited by 197 publications

References 108 publications

Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances

Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances

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

Dynamic stereoselective annulation via aldol-oxa-cyclization cascade reaction to afford spirooxindole pyran polycycles

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