HFIP in Organic Synthesis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 12544 - 12747

Published: July 17, 2022

1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability stabilize ionic species, transfer protons, and engage range of other intermolecular interactions. The use this exponentially increased the past decade become choice some areas, such as C–H functionalization chemistry. In review, following brief history HFIP an overview physical properties, literature examples reactions using or additive are presented, emphasizing effect each reaction.

Language: Английский

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Highly Diastereo- and Enantioselective Synthesis of Tetrahydrobenzo[b]azocines via Palladium-Catalyzed [4 + 4] Cycloaddition

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(5), P. 2684 - 2690

Published: Feb. 12, 2021

The construction of N-heterocyclic eight-membered rings with good regio-, stereo-, and enantioselective control remains a formidable challenge in asymmetric catalysis. Herein, we report palladium-catalyzed [4 + 4] cycloaddition anthranils γ-methylidene-δ-valerolactones the presence Et3B, delivering highly functionalized tetrahydrobenzo[b]azocine derivatives high efficiency diastereoselectivities enantioselectivities (up to 92% yield, 20:1 dr, 99% ee). Moreover, complex substrates derived from natural products (bearing different functionalities) could be well-tolerated catalytic cycloaddition. mild reaction conditions, conjunction broad substrate scope (44 examples), level stereoselectivity, provide great potential build azocine compounds simple building blocks.

Language: Английский

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Construction of bridged polycycles through dearomatization strategies

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(18), P. 3960 - 3982

Published: Jan. 1, 2021

Bridged polycycles are privileged molecular skeletons with wide occurrence in bioactive natural products and pharmaceuticals. Therefore, they have been the pursing target molecules of numerous chemists. The rapid convenient generation sp3-rich complex three-dimensional from simple easily available aromatics has made dearomatization a highly valuable synthetic tool for construction rigid challenging bridged rings. This review summarizes the-state-of-the-art advances strategies application ring formation, discusses their advantages limitations in-depth mechanism, highlights value total synthesis products. We wish this will provide an important reference medicinal chemists inspire further development intriguing research area.

Language: Английский

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α-Halogenoacetamides: versatile and efficient tools for the synthesis of complex aza-heterocycles

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(37), P. 8467 - 8485

Published: Jan. 1, 2019

This review presents the use of α-alkyl- and α-alkoxy-halogenoacetamides as powerful partners for domino 1,3-dipolar cycloaddition reactions resulting in a ring closure.

Language: Английский

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Anthranils: versatile building blocks in the construction of C–N bonds and N-heterocycles

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(9), P. 1177 - 1196

Published: Jan. 1, 2020

This review article provides an overview of the recent progress in transformations anthranils, which have emerged as versatile building blocks assembly various C–N bonds and medicinally active heterocyclic systems.

Language: Английский

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Synthetic aspects of 1,4- and 1,5-benzodiazepines usingo-phenylenediamine: a study of past quinquennial

RSC Advances, Journal Year: 2023, Volume and Issue: 13(6), P. 3694 - 3714

Published: Jan. 1, 2023

This paper presents recent evolutions in the synthetic aspects of 1,5- and 1,4-benzodiazepines using o -phenylenediamine as a precursor provides an up-to-date review findings (2018–2022).

Language: Английский

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Advances in [4+3]‐Annulation/Cycloaddition Reactions Leading to Homo‐ and Heterocycles with Seven‐Membered Rings

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(16), P. 2380 - 2402

Published: June 10, 2020

In this review, we summarize advances in [4+3] and a few other annulation/cycloaddition reactions for the construction of seven membered rings, with an emphasis on literature subsequent to year 2010. The type products include following: azepines, diazepines, benzazepinones, 1,2-diazepinones, oxazepinones, benzothiazepines, benzodiazepinones, benzoxopinones, cyclohepta[b]indoles, benzoxazepines, azepino-indoles, oxepines/oxazepanes, triazepines oxepinoindolones/azepinoindolones, oxadiazepines, azabicyclooctanes. Emphasis is also given cover diverse types annulations; possible intermediates are displayed illustrated schemes aid future work.

Language: Английский

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Rapid Access to Hindered α-Amino Acid Derivatives and Benzodiazepin-3-ones from Aza-Oxyallyl Cations

Organic Letters, Journal Year: 2020, Volume and Issue: 22(4), P. 1420 - 1425

Published: Jan. 17, 2020

Catalyst-free and mild synthetic methods for the construction of hindered α-amino acid derivatives are presented herein. A wide range amino amides can be readily obtained from reaction α-halohydroxamates with a variety amines, including anilines, primary secondary amines. Moreover, aza/aza-[4+3] cycloaddition in situ-generated aza-oxyallyl cations 2-aminophenyl α,β-unsaturated carbonyls to furnish seven-membered benzodiazepin-3-ones is reported first time.

Language: Английский

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Organocatalytic Enantioselective [4+3]‐Cycloadditions of Azaoxyallyl Cations with 2‐Aminophenyl Enones

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(17), P. 4197 - 4203

Published: July 12, 2021

Abstract The first organocatalytic asymmetric [4+3]‐cycloaddition of 2‐aminophenyl α,β‐unsaturated carbonyls with in situ generated azaoxyallyl cations was developed, and enantioenriched functionalized seven‐membered 1,4‐benzodiazepine‐3‐ones were obtained good yields excellent enantioselectivities. This approach also extended to the δ‐hydroxy carbonyls, affording 1,4‐oxazepanes one step under mild conditions. Several novel adducts demonstrated promising bioactivity prevention peripheral nerve degeneration. magnified image

Language: Английский

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α‐Halocarbonyls as a Valuable Functionalized Tertiary Alkyl Source

ChemistryOpen, Journal Year: 2024, Volume and Issue: unknown

Published: July 11, 2024

Abstract This review introduces the synthetic organic chemical value of α‐bromocarbonyl compounds with tertiary carbons. compound a carbon has been used primarily only as radical initiator in atom transfer polymerization (ATRP) reactions. However, recent development photo‐radical reactions (around 2010), research on use alkyl precursors became popular 2012). As more examples were reported, studied not radicals but also for their applications organometallic and ionic That is, act nucleophiles well electrophiles. The carbonyl group is attractive because it allows skeleton to be converted after reaction, being applied total synthesis. In our survey until 2022, can perform full range necessary synthesis, including multi‐component reactions, cross‐coupling, substitution, cyclization, rearrangement, stereospecific asymmetric α‐Bromocarbonyl have created new trend alkylation, which then had limited reaction patterns focuses how chemistry.

Language: Английский

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