Asymmetric Tandem 1,5‐Hydride Shift/Ring Closure for the Synthesis of Chiral Spirooxindole Tetrahydroquinolines

Cao, Weidi; Liu, Xiaohua; Guo, Jing; Lin, Lili; Feng, Xiaoming

doi:10.1002/chem.201404327

Cited by 82 publications

(25 citation statements)

References 73 publications

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“…via asymmetric intramolecular 1,5‐hydride transfer/closure of oxindole derivatives 237 in the presence of chiral N , N ’‐dioxide–metal complexes (Sc(OTf) 2 , L 1 ) 238 in dichloroethane at 35 °C (Scheme 47). [63] The authors confirmed that this method is upscalable to gram level (3 mmol) without significant decrease in yield and diastereo‐ and enantioselectivity.…”

Section: C1‐functionalization With Annulationmentioning

confidence: 65%

C1‐Functionalization of 1,2,3,4‐Tetrahydroisoquinolines (THIQs)

et al. 2021

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1,2,3,4‐tetrahydroisoquinoline (THIQ) and its derivatives possess a widespread biochemical, pharmaceutical and biological properties and they are the key building blocks in the structure of drugs and natural alkaloids. Accordingly, construction of multi‐substituted and polycyclic THIQs through functionalization of THIQs at different positions especially at C1‐position have come to the center of attraction in recent studies. In this review, we've focused on the classification of C1‐functionalization of THIQs in the research articles from 2013 on, including a brief description of the reaction mechanisms for the synthesis of multi‐substituted and polycyclic THIQs based on the type of substituents at the 1‐position of the THIQ moiety. From this point of view, the main categories are C1‐Functionalization and C1‐Functionalization with annulation.

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Section: C1‐functionalization With Annulationmentioning

confidence: 65%

C1‐Functionalization of 1,2,3,4‐Tetrahydroisoquinolines (THIQs)

et al. 2021

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“…For example, EWG in positions 5 and 6 decrease the performance of the cycloaddition and require higher catalyst loading over isatin- dioxide XX-Sc(OTf)3 complex promoted the reaction with up to 97% yields and >20:1 diastereoselectivities. 29 Notably, partial self disproportionation of enantiomers (SDE) occurs during silica column purification of the products (Scheme 22). 32 The reaction comprised allylic carbonate tethered pyrroles or indoles (98) 33 in the presence of [Ir(cod)Cl]2 and phosphoramidite XXIII as the ligand.…”

Section: Scandium-catalysed Methodologies 25mentioning

confidence: 99%

New development in the enantioselective synthesis of spiro compounds

et al. 2018

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The enantioselective synthesis of spirocycles has long been pursued by organic chemists. Despite their unique 3D properties and presence in several natural products, the difficulty in their enantioselective synthesis makes them underrepresented in pharmaceutical libraries. Since the first pioneering reports of the enantioselective construction of spirosilanes by Tamao et al., significant effort has been devoted towards the development of new promising asymmetric methodologies. Remarkably, with the advent of organocatalysis, particularly over six years, the reported methodologies for the synthesis of spirocycles have increased exponentially. The aim of this review is to summarize the latest trends and developments in the enantioselective synthesis of spirocompounds during these last six years.

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“…In 2015, Feng’s group developed an asymmetric tandem [1,5]-hydride shift/cyclization reaction to produce chiral spirooxindole tetrahydroquinolines using chiral N , N ′-dioxide/Sc(OTf) 3 as a catalytic system ( Scheme 1 ) ( Cao et al, 2015 ). As far as we know, this is the only report for the asymmetric version of tandem [1,5]-hydride shift/cyclization.…”

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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Asymmetric Tandem 1,5‐Hydride Shift/Ring Closure for the Synthesis of Chiral Spirooxindole Tetrahydroquinolines

Cited by 82 publications

References 73 publications

C1‐Functionalization of 1,2,3,4‐Tetrahydroisoquinolines (THIQs)

C1‐Functionalization of 1,2,3,4‐Tetrahydroisoquinolines (THIQs)

New development in the enantioselective synthesis of spiro compounds

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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