Recent Advances in Catalytic Asymmetric Construction of Atropisomers

Chemical Reviews, Год журнала: 2021, Номер 121(8), С. 4805 - 4902

Опубликована: Март 27, 2021

Atropisomerism is a stereochemical behavior portrayed by three-dimensional molecules that bear rotationally restricted σ bond. Akin to the well-represented point-chiral molecules, atropisomerically chiral compounds are finding increasing utilities in many disciplines where molecular asymmetry influential. This provides steady demand on atroposelective synthesis, numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods while expanding structural diversity of atropisomers. review summarizes key achievements stereoselective preparation biaryl, heterobiaryl, nonbiaryl atropisomers documented between 2015 2020. Emphasis placed strategies for each class, examples cited illustrate potential applications accessed atropochiral targets.

Язык: Английский

---

Catalytic Asymmetric Construction of Axially Chiral Indole‐Based Frameworks: An Emerging Area

Chemistry - A European Journal, Год журнала: 2020, Номер 26(68), С. 15779 - 15792

Опубликована: Май 4, 2020

Axially chiral indole-based frameworks have been recognized as a class of important five-membered heterobiaryls and developing catalytic asymmetric approaches for constructing these in an enantioselective manner is highly desirable. In recent years, synthetic chemists paid much attention to this research field, rapid developments occurred. At point, range axially scaffolds constructed via various reactions based on different strategies. Thus, the construction has become emerging area. This minireview summarizes advances field gives some insights into future developments, which will help thrive.

Язык: Английский

---

Carbene‐Catalyzed Asymmetric Construction of Atropisomers

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(50), С. 26026 - 26037

Опубликована: Июль 16, 2021

Atropisomeric molecules have found proven applications and shown promising potential in chemistry medicine. The design of N-heterocyclic carbene (NHC) catalyzed reactions to construct atropisomerically enriched has emerged as an important research topic recent years. These include kinetic resolutions, asymmetric desymmetrizations, central-to-axial chirality conversions, cycloadditions. This Minireview evaluates summarizes the progress NHC-based organic catalysis for access atropisomers, briefly states our personal perspectives on future advancement this topic. NHC provided rich unique reaction modes that led success synthesis central-chiral molecules. It is expected similar could also be achieved developing prepare atropisomeric molecules, including those not easily accessible by other methods.

Язык: Английский

---

Atroposelective Access to Oxindole-Based Axially Chiral Styrenes via the Strategy of Catalytic Kinetic Resolution

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(37), С. 15686 - 15696

Опубликована: Авг. 26, 2020

Atroposelective synthesis of axially chiral molecules has attracted substantial attention from chemists because the importance such molecules. However, catalytic asymmetric styrenes or vinyl arenes is underdeveloped and challenging due to low rotational barrier weak configurational stability Therefore, development powerful strategies for atroposelective great importance. In this work, we have accomplished first access oxindole-based by strategy kinetic resolution, offered two kinds styrene derivatives in good diastereoselectivities (up 94:6 dr) excellent enantioselectivities 98% ee) with high selectivity factors (S up 106). This not only provides easy but also offers a robust method synthesizing bisamide bearing both axial central chirality. More importantly, added new class members atropisomeric family, especially family styrenes.

Язык: Английский

---

Organocatalytic Atroposelective Synthesis of N−N Axially Chiral Indoles and Pyrroles by De Novo Ring Formation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(17)

Опубликована: Янв. 26, 2022

Abstract The first highly atroposelective construction of N−N axially chiral indole scaffolds was established via a new strategy de novo ring formation. This makes use the organocatalytic asymmetric Paal–Knorr reaction well‐designed N ‐aminoindoles with 1,4‐diketones, thus affording ‐pyrrolylindoles in high yields and excellent atroposelectivities (up to 98 % yield, 96 ee). In addition, this is applicable for synthesis bispyrroles 97 More importantly, such heterocycles can be converted into organocatalysts applications catalysis, some molecules display potent anticancer activity. work not only provides but also offers members atropisomer family promising synthetic medicinal chemistry.

Язык: Английский

---

Recent Progress toward the Construction of Axially Chiral Molecules Catalyzed by an N-heterocyclic Carbene

ACS Catalysis, Год журнала: 2021, Номер 11(20), С. 12520 - 12531

Опубликована: Сен. 28, 2021

Axial chirality widely exists in natural products, pharmaceutical compounds, and other functional molecules; these axially chiral compounds also find wide utility as catalysts or ligands organic synthetic chemistry. Nevertheless, whereas significant progress has been made toward the synthesis of enantioenriched molecules over past two decades, strategies involving organocatalysis have only started to emerge recently. N-heterocyclic carbene (NHC) organocatalysts recognized be powerful tools for rapid construction complex molecular architectures. However, previous works mainly focused on assembly point recently it realized that asymmetric axial could achieved by using NHCs organocatalysts. This Perspective highlights developments advances scaffolds catalyzed NHCs. The aim this is provide an overview area serve a stepping stone future investigations.

Язык: Английский

---

Catalytic Asymmetric Synthesis of Axially Chiral 3,3'‐Bisindoles by Direct Coupling of Indole Rings

Chinese Journal of Chemistry, Год журнала: 2022, Номер 40(18), С. 2151 - 2160

Опубликована: Май 31, 2022

Comprehensive Summary A new strategy for the enantioselective synthesis of axially chiral 3,3'‐bisindoles was devised by direct coupling two indole rings. This makes use C3‐umpolung reactivity 2‐indolylmethanols, which enables catalytic asymmetric addition reaction 2‐indolylmethanols with rationally designed 2‐substituted indoles, thus constructing 3,3'‐bisindole scaffolds in overall excellent yields (up to 98%) high enantioselectivities 96 : 4 er). approach not only has overcome challenges five‐five‐membered heterobiaryls, but also represents a application catalysis. More importantly, this class can undergo variety post‐functionalizations give 3,3'‐bisindole‐based organocatalysts, have found their preliminary applications

Язык: Английский

---

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Ноя. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Язык: Английский

---

Atroposelective Synthesis of 1,1′‐Bipyrroles Bearing a Chiral N−N Axis: Chiral Phosphoric Acid Catalysis with Lewis Acid Induced Enantiodivergence

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(16)

Опубликована: Фев. 17, 2022

Abstract We present herein a highly efficient atroposelective synthesis of axially chiral 1,1′‐bipyrroles bearing an N−N linkage from simple hydrazine and 1,4‐diones. Further product derivatizations led to bifunctional compounds with high potential in asymmetric catalysis. For this chrial phosphoric acid (CPA)‐catalyzed double Paal–Knorr reaction, intriguing Fe(OTf) 3 ‐induced enantiodivergence was also observed.

Язык: Английский

---

Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(13), С. 6040 - 6049

Опубликована: Март 24, 2022

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged ligand/catalysts, optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable intriguing strategy but are far less developed. Moreover, efficient synthesis axially heterobiaryl molecules, especially ones having multiple heteroatoms other types elements, through radical routes remains extremely limited. We herein disclose first catalytic asymmetric, metal-free construction centrally by Minisci reaction 5-arylpyrimidines α-amino acid-derived redox-active esters. This is enabled use 4CzIPN as an organic photoredox catalyst conjunction a phosphoric acid catalyst. The achieved variety interesting featuring union α-branched amine generally excellent regio-, diastereo-, enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). finding also builds up new platform development desymmetrization methods via radical-involved atroposelective functionalization at heteroarene prochiral heterobiaryls.

Язык: Английский

---