Aromatization-Driven Cascade [1,5]-Hydride Transfer/Spirocyclization Promoted by Fluorinated Alcohols

Lv, Xintong; Hu, Fangzhi; Duan, Kang; Li, Shuaishuai; Liu, Qing; Xiao, Jian

doi:10.1021/acs.joc.8b02754

Cited by 60 publications

(12 citation statements)

References 95 publications

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“…Later on, a cascade [1,5]‐hydride transfer/dearomative cyclization of the prepared p ‐QMs 86 was also developed by our group (Scheme ) . This HFIP‐mediated dearomative reaction worked well, generating azaspiro‐cyclohexadienones 88 in high efficiency.…”

Section: Dearomatization Reactionsmentioning

confidence: 97%

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Xiao

2019

The Chemical Record

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109

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Fluorinated alcohols have been widely used in the synthetic organic chemistry over the past decades. The unique properties such as the strong hydrogen‐bonding donor ability and low nucleophilicity allow them to promote organic reactions in the absence of any catalyst. These approaches have distinct advantages in terms of operational simplicity, practicability and environmental friendliness. Reactions promoted by fluorinated alcohols, including nucleophilic substitution reactions, annulation reactions, electrophilic reactions, dearomatization reactions, functionalization of multiple bond, epoxidation reactions and miscellaneous reactions have been summarized in this account.

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Section: Dearomatization Reactionsmentioning

confidence: 97%

Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

Xiao

2019

The Chemical Record

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109

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“…In 2019, based on previous works, the same group continued to use HFIP as the solvent to develop p -QMs-triggered cascade [1,5]-hydride shift/spirocyclization and hydrolysis reaction. This strategy enabled the synthesis of spirocyclic products 181 with good to high yields (52%–99%) under mild conditions, featuring room temperature, additive-free, and good functional group tolerance ( Scheme 19 ) ( Lv et al, 2019 ). Interestingly, an array of ortho -benzylated anilines 183 were obtained with high yields when using acyclic amines incorporating N,N ′-dibenzyl, N -methyl- N ′-benzyl, and N,N ′-diethyl groups.…”

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

confidence: 99%

“…As one of the most common and effective C(sp 3 )-H functionalization methodologies, the cascade [1,5]-hydride shift/cyclization strategy possessed an inherent advantage in the transformation of unreactive functional groups or bonds to various chemical structures. However, building structurally complex spiro-tetrahydroquinoline via the cascade [1,5]-hydride shift/cyclization strategy has rarely been established before the limited but significant works ( Pastine and Sames, 2005 ; Kang et al, 2010 ; Cao et al, 2011 ; Wang, 2013 ; Mori et al, 2015 ; Zhu et al, 2017 ; Lv et al, 2019 ). More importantly, rarely an updated review has systematically summarized these important progresses despite scattered reports documented in several reviews ( Wang and Xiao, 2014 ; Wang and Xiao, 2016 ; Xiao Mingyan et al, 2018 ; An and Xiao, 2021 ).…”

Section: Introductionmentioning

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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“…[6] However, the limited kinds of o-QMs and dienophiles restrict their applications in the assembly of molecular diversity and complexity, which posed a formidable challenge. [7] As a continuation of our research interest in one-step assembly of biological active molecules, [8] herein, we reported an organocatalytic dearomative [4 + 2] cycloaddition of oxindole-embedded o-QMs with 2,5-dialkylfurans, furnishing the pharmaceutically important spiro[chroman-4,3'-oxindole] scaffolds in high yields with excellent diastereoselectivities under mild conditions. In this strategy, 2,5-dialkylfurans would act as novel dienophiles while oxindole- embedded o-QMs serve as new four-membered building blocks.…”

mentioning

confidence: 99%

“…However, it is noteworthy that a competitive conjugate addition of electron-rich 2,5-dialkylfurans to o-QMs might take place. [7] As a continuation of our research interest in one-step assembly of biological active molecules, [8] herein, we reported an organocatalytic dearomative [4 + 2] cycloaddition of oxindole-embedded o-QMs with 2,5-dialkylfurans, furnishing the pharmaceutically important spiro[chroman-4,3'-oxindole] scaffolds in high yields with excellent diastereoselectivities under mild conditions.…”

mentioning

confidence: 99%