The asymmetric synthesis of polycyclic 3-spirooxindole alkaloids via the cascade reaction of 2-isocyanoethylindoles

Zhao, Xiaohu; Liu, Xiaohua; Xiong, Qian; Mei, Hongjiang; Ma, Buyong; Lin, Lili

doi:10.1039/c5cc06353a

Cited by 70 publications

(23 citation statements)

References 75 publications

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“…Domino reactions hold a prominent place in modern synthetic methodology through the atom economic formation of complex compounds, and more recently with high enantioselective control over chiral centers. In some cases multiple asymmetric centers are created with extremely good enantioselectivities reaching as high as 99% ee in many cases [141][142][143][144][145][146][147][148]. A broad range of products result from this type of reactivity such as (hydroxyalkyl)tetrazoles, (hydroxyalkyl)oxazoles and diamino acids, which are discussed here, amongst others.…”

Section: Domino Reactions | 21mentioning

confidence: 99%

Enantioselective Main Group Catalysis: Modern Catalysts for Organic Transformations

Wilkins

Melen

2016

Coordination Chemistry Reviews

116

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Contents 1. Introduction………………………………………………………………………………………………... 1 2. Group 2-catalyzed Mannich reactions…………………………………………………………………...... 3 3. Group 2-catalyzed 1,4-addition reactions…………………………………………………………………. 5 4. Silylation of ketones and imines…………………………………………………………………………... 8 5. Hydrogenation reactions using group 13 Lewis acids and frustrated Lewis pairs…………………………12 6. Hydroamination reactions with s-block elements………………………………………………………… 14 7. Aluminum-centered catalysts in phosphonylation reactions……………………………………………… 17 8. Domino reactions…………………………………………………………………..……………………….21 9. Conclusions……………………………………………………………………………………………….. 24 This review highlights a number of recent developments in the field of main group enantioselective catalysis. Many essential transformations can be effected catalytically such as hydrosilylation, hydroamination and hydrogenation reactions, amongst others, in an asymmetric fashion using earth abundant sand p-block elements such as calcium, strontium, boron and aluminum. Recent work in this area has shown that these systems are not only active in catalysis but may also have the potential to compete with transition metal based systems with the reduced cost and toxicity often associated with main group chemistry. Keywords: enantioselective main group catalysis chiral asymmetric | 7 Scheme 8. Catalytic malonate addition reaction using calcium PyBOX complex [66]. Scheme 9. Proposed catalytic cycle of calcium-catalyzed addition reaction to nitro-styrene [66].

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Section: Domino Reactions | 21mentioning

confidence: 99%

Enantioselective Main Group Catalysis: Modern Catalysts for Organic Transformations

Wilkins

Melen

2016

Coordination Chemistry Reviews

116

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“…3‐(2‐Isocyanoethyl)indoles, which possess several reactive sites, are known to readily undergo cascade cyclization reactions with Michael acceptors,– imines– or isocyanates, leading to the formation of [6,5,5,5] tetracyclic spiroindoline skeleton (Scheme a). However, all of these cascade processes work with only a single reaction mode involving the electrophilic nitrilium ion intermediate.…”

Section: Figurementioning

confidence: 99%

Tandem Cross‐Coupling/Spirocyclization/Mannich‐Type Reactions of 3‐(2‐Isocyanoethyl)indoles with Diazo Compounds toward Polycyclic Spiroindolines

Chen

Luo

et al. 2019

Angewandte Chemie

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Tandem reactions of Pd‐catalyzed cross‐coupling of 3‐(2‐isocyanoethyl)indoles with diazoacetates and subsequent spirocyclization/Mannich‐type reaction have been developed to assemble polycyclic spiroindoline skeletons. Formation of spiroindolenines has been proven as the crucial step for the following Mannich‐type cyclization reaction. Accordingly, a novel approach on chiral phosphoric acid catalyzed Mannich‐type cyclization toward the formation of diastereomerically and enantiomerically enriched pentacyclic spiroindolines has been established. Moreover, the products of the reaction are versatile building blocks in synthetic chemistry, as demonstrated by the synthesis of the key framework of aspidosperma and kopsia alkaloids.

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“…The same authors also applied this catalyst system to the asymmetric domino Michael/Friedel–Crafts/Mannich reaction of variously substituted 2‐isocyanoethylindoles 39d–n with a 3‐alkenyloxindole such as ( E )‐1‐Boc‐3‐ tert ‐butylideneindolinone 20v 30. In this case, the reaction was performed in DCE at 0 °C to provide a straightforward access to a series of chiral polycyclic 3‐spirooxindoles 44a–k bearing cyclopenta[ b ]indole units with four contiguous stereocenters in high yields (75–96%), and enantioselectivities of 73–93% ee , combined with moderate to high diastereoselectivities of 38 to >90% de (Scheme ).…”

Section: Enantioselective Metal‐catalyzed Mono‐ and Two‐component Dmentioning

confidence: 99%

Recent Developments in Enantioselective Metal‐Catalyzed Domino Reactions

Pellissier

2016

Adv Synth Catal

106

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International audienceThis review updates the major progress in the field of enantioselective one-, two-, and multicomponent domino reactions promoted by chiral metal catalysts, covering the literature since the beginning of 2012. It illustrates how enantioselective metal-catalyzed processes have emerged as outstanding tools for the development of a wide variety of fascinating one-pot asymmetric domino reactions, allowing complex and diverse structures to be easily generated from simple materials in a single step. During the last 4 years, a myriad of already existing as well as completely novel and powerful asymmetric domino processes have been developed on the basis of asymmetric metal catalysis, taking economical advantages, such as avoiding costly protecting groups and time-consuming purification procedures after each step

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The asymmetric synthesis of polycyclic 3-spirooxindole alkaloids via the cascade reaction of 2-isocyanoethylindoles

Cited by 70 publications

References 75 publications

Enantioselective Main Group Catalysis: Modern Catalysts for Organic Transformations

Enantioselective Main Group Catalysis: Modern Catalysts for Organic Transformations

Tandem Cross‐Coupling/Spirocyclization/Mannich‐Type Reactions of 3‐(2‐Isocyanoethyl)indoles with Diazo Compounds toward Polycyclic Spiroindolines

Recent Developments in Enantioselective Metal‐Catalyzed Domino Reactions

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