Cascade [1,5]-Hydride Transfer/Cyclization for Synthesis of [3,4]-Fused Oxindoles

Zhu, Shuai; Chen, Chunqi; Duan, Kang; Sun, Yun-Ming; Li, Shuaishuai; Liu, Qing; Xiao, Jian

doi:10.1021/acs.joc.9b00489

Cited by 33 publications

(8 citation statements)

References 77 publications

(37 reference statements)

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“…It is well developed for the construction of C−C, [5] C−O [5b,6] or C−N [7] bonds and offers rapid access to polycyclic compounds. [1,n]‐HT/cyclization occurs under either thermal conditions [7b] or the catalysis of Lewis acids [5c,e,8] and Brønsted acids [5d,7c,9] …”

Section: Methodsmentioning

confidence: 99%

Diastereoselective Bidirectional C(sp³)−H Bond Functionalization of Piperazine Compounds

et al. 2022

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A highly diastereoselective bidirectional C(sp3)−H bond functionalization of piperazine compounds, triggered by a Lewis acid catalyzed sequential hydride shift/cyclization process, is reported. Catalysts and ligands are key factors that control the diastereoselectivity of the reaction. The reaction affords the product with good yield and high diastereoselectivity. Detailed investigation of the reaction mechanism reveals that the energy barrier between the cis products and trans products results in the diastereoselectivity of the reaction. The trans products, which have higher energy and which are generated from the cis products, act as intermediate products.

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Section: Methodsmentioning

confidence: 99%

Diastereoselective Bidirectional C(sp³)−H Bond Functionalization of Piperazine Compounds

et al. 2022

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“…In 2019, Li and Xiao developed racemic domino Knoevenagel/[1,5]-hydride transfer/cyclization reactions between C4-amine-substituted isatins 148 and cyclic 1,3-dicarbonyl compound 149 catalyzed by Sc(OTf) 3 which produced the corresponding tricyclic [3,4]-fused oxindoles 150. [45] As shown in Scheme 38, the two substrates underwent a Knoevenagel condensation to give the corresponding α,β-unsaturated ketone intermediate AB. Then, the latter was submitted to a [1,5]-hydride transfer which afforded zwitterionic iminium intermediate AC, which subsequently underwent an intramolecular cyclization to provide the final domino product.…”

Section: Enantioselective Scandium-catalyzed Domino Reactionsmentioning

confidence: 99%

“…In 2019, Li and Xiao developed racemic domino Knoevenagel/[1,5]‐hydride transfer/cyclization reactions between C4‐amine‐substituted isatins 148 and cyclic 1,3‐dicarbonyl compound 149 catalyzed by Sc(OTf) 3 which produced the corresponding tricyclic [3,4]‐fused oxindoles 150 [45] . As shown in Scheme 38, the two substrates underwent a Knoevenagel condensation to give the corresponding α,β‐unsaturated ketone intermediate AB .…”

Section: Enantioselective Scandium‐catalyzed Domino Reactionsmentioning

confidence: 99%

Recent Developments in Enantioselective Domino Reactions. Part B: First Row Metal Catalysts

Pellissier

2023

Adv Synth Catal

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This review updates the field of enantioselective domino reactions promoted by chiral catalysts derived from first row metals, such as zinc, iron, copper, scandium, nickel, cobalt, titanium, chromium and magnesium as special case, published since the beginning of 2019. It illustrates how much a diversity of these catalysts allow an impressive range of novel highly enantioselective domino reactions of many types to be achieved, providing a one‐pot access to very complex and functionalized chiral molecules from simple starting materials.

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“…Soon after, Xiao’s group uncovered the scandium-catalyzed redox-neutral cascade [1,5]-hydride shift/cyclization of C4-amine-substituted isatins 24 and 1,3-dicarbonyl compounds 25 ( Scheme 4 ) ( Zhu et al, 2019 ). In this process, the α,β-unsaturated 1,3-dicarbonyl intermediate 29 acted as a hydride acceptor.…”

Section: The Construction Of a Spiro-tetrahydroquinoline Skeleton Con...mentioning

confidence: 99%

The Cascade [1,5]-Hydride Shift/Intramolecular C(sp3)–H Activation: A Powerful Approach to the Construction of Spiro-Tetrahydroquinoline Skeleton

Quan

Xie

et al. 2022

Front. Chem.

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The direct functionalization of inert C–H bonds is regarded as one of the most powerful strategies to form various chemical bonds and construct complex structures. Although significant advancements have been witnessed in the area of transition metal-catalyzed functionalization of inert C–H bonds, several challenges, such as the utilization and removal of expensive transition metal complexes, limited substrate scope and large-scale capacity, and poor atom economy in removing guiding groups coordinated to the transition metal, cannot fully fulfill the high standard of modern green chemistry nowadays. Over the past decades, due to its inherent advantage compared with a transition metal-catalyzed strategy, the hydride shift activation that applies “tert-amino effect” into the direct functionalization of the common and omnipresent C(sp3)–H bonds adjacent to tert-amines has attracted much attention from the chemists. In particular, the intramolecular [1,5]-hydride shift activation, as the most common hydride shift mode, enables the rapid and effective production of multifunctionally complex frameworks, especially the spiro-tetrahydroquinoline derivatives, which are widely found in biologically active natural products and pharmaceuticals. Although great accomplishments have been achieved in this promising field, rarely an updated review has systematically summarized these important progresses despite scattered reports documented in several reviews. Hence, in this review, we will summarize the significant advances in the cascade [1,5]-hydride shift/intramolecular C(sp3)-H functionalization from the perspective of “tert-amino effect” to build a spiro-tetrahydroquinoline skeleton, and the content is categorized by structure type of final spiro-tetrahydroquinoline products containing various pharmaceutical units. Besides, current limitations as well as future directions in this field are also pointed out. We hope our review could provide a quick look into and offer some inspiration for the research on hydride shift strategy in the future.

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Cascade [1,5]-Hydride Transfer/Cyclization for Synthesis of [3,4]-Fused Oxindoles

Cited by 33 publications

References 77 publications

Diastereoselective Bidirectional C(sp³)−H Bond Functionalization of Piperazine Compounds

Diastereoselective Bidirectional C(sp³)−H Bond Functionalization of Piperazine Compounds

Recent Developments in Enantioselective Domino Reactions. Part B: First Row Metal Catalysts

The Cascade [1,5]-Hydride Shift/Intramolecular C(sp3)–H Activation: A Powerful Approach to the Construction of Spiro-Tetrahydroquinoline Skeleton

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Cascade [1,5]-Hydride Transfer/Cyclization for Synthesis of [3,4]-Fused Oxindoles

Cited by 33 publications

References 77 publications

Diastereoselective Bidirectional C(sp3)−H Bond Functionalization of Piperazine Compounds

Diastereoselective Bidirectional C(sp3)−H Bond Functionalization of Piperazine Compounds

Recent Developments in Enantioselective Domino Reactions. Part B: First Row Metal Catalysts

The Cascade [1,5]-Hydride Shift/Intramolecular C(sp3)–H Activation: A Powerful Approach to the Construction of Spiro-Tetrahydroquinoline Skeleton

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Diastereoselective Bidirectional C(sp³)−H Bond Functionalization of Piperazine Compounds

Diastereoselective Bidirectional C(sp³)−H Bond Functionalization of Piperazine Compounds