Organocatalytic Higher-Order [8+2] Cycloaddition for the Assembly of Atropoenantiomeric 3-Arylindolizines

Yang, Guang; Li, Zhipeng; Liu, Yuhan; Guo, Donghui; Sheng, Xijun; Wang, Jian

doi:10.1021/acs.orglett.1c03220

Cited by 19 publications

(12 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Notable catalytic approaches are Shi's Pd‐catalyzed state‐of‐the‐art atroposelective C−H functionalization strategy enabled by a transient chiral auxiliary [7g, 8, 9] (Scheme 1c). Very recently, Wang and co‐workers developed organo‐catalyzed atroposelective [8+2] cycloaddition of pyridinium ylides with ynals, providing axially chiral 4‐formy‐3‐arylindolizines [10] . Despite those significant processes, the development of a novel methodology for creating highly enantioenriched axially chiral aldehydes is extremely attractive.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Axially Chiral Aldehydes by N‐Heterocyclic‐Carbene‐Catalyzed Desymmetrization Followed by Kinetic Resolution

Sun

et al. 2022

Angew Chem Int Ed

View full text Add to dashboard Cite

Axially chiral aldehydes have received increasing attention in enantioselective catalysis. However, only very few catalytic methods have been developed to construct structurally diverse axially chiral aldehydes. We herein describe an NHC-catalyzed atroposelective esterification of biaryl dialdehydes as a general and practical strategy for the construction of axially chiral aldehydes. Mechanistic studies indicate that coupling proceeds through a novel combination of NHC-catalyzed desymmetrization of the dialdehydes and kinetic resolution. This protocol features excellent enantioselectivity, mild conditions, good functional-group tolerance, and applicability to late-stage functionalization and provides a modular platform for the synthesis of axially chiral aldehydes and their derivatives.

show abstract

Section: Methodsmentioning

confidence: 99%

Synthesis of Axially Chiral Aldehydes by N‐Heterocyclic‐Carbene‐Catalyzed Desymmetrization Followed by Kinetic Resolution

Sun

et al. 2022

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

“…Later, Wang and co-workers presented the amine L25 -catalyzed higher-order [8 + 2] cycloaddition of pyridinium ylides 83 with 82 via Michael addition and intramolecular cyclization, furnishing an array of 3-arylindolizines 84 with broad functional group compatibilities ( Scheme 26 ) [ 91 ].…”

Section: Synthesis Of Axially Chiral Heterobiaryl Scaffold Catalyzed ...mentioning

confidence: 99%

Advances in Atroposelectively De Novo Synthesis of Axially Chiral Heterobiaryl Scaffolds

et al. 2022

View full text Add to dashboard Cite

Axially chiral heterobiaryl frameworks are privileged structures in many natural products, pharmaceutically active molecules, and chiral ligands. Therefore, a variety of approaches for constructing these skeletons have been developed. Among them, de novo synthesis, due to its highly convergent and superior atom economy, serves as a promising strategy to access these challenging scaffolds including C–N, C-C, and N-N chiral axes. So far, several elegant reviews on the synthesis of axially chiral heterobiaryl skeletons have been disclosed, however, atroposelective construction of the heterobiaryl subunits by de novo synthesis was rarely covered. Herein, we summarized the recent advances in the catalytic asymmetric synthesis of the axially chiral heterobiaryl scaffold via de novo synthetic strategies. The related mechanism, scope, and applications were also included.

show abstract

“…In 1996, Theil and co-workers obtained axially chiral bisindolizines through the lipase-catalyzed acylative kinetic resolution of diols . Very recently, the groups of Feng and Wang realized the construction of atropoenantiomeric 2-arylindolizines via reactions of pyridinium ylides catalyzed by a chiral amine catalyst and N , N ′-dioxide–earth metal complexes, respectively. Our group previously developed an organocatalytic desymmetrization of cyclopentendiones to access axially chiral C3-alkenyl indolizines in a one-pot process (Scheme c, left) .…”

mentioning

confidence: 99%

Chiral Phosphoric Acid-Catalyzed Asymmetric Arylation of Indolizines: Atroposelective Access to Axially Chiral 3-Arylindolizines

et al. 2022

View full text Add to dashboard Cite

We report herein a highly straightforward strategy for the synthesis of a new axially chiral 3-arylindolizine scaffold via organocatalytic asymmetric arylation reactions of indolizines and p-quinone esters. Using the chiral phosphoric acid catalyst, a series of axially chiral 3-arylindolizines were accessed in good to excellent yields and atropo-enantioselectivities. This approach features a broad substrate scope, mild reaction conditions, good scalability, and facile derivatization. Moreover, preliminary investigations based on nonlinear effects and a thermal racemization study demonstrated the intrinsic pathway for the formation of axial chirality and its potential utility.

show abstract

Organocatalytic Higher-Order [8+2] Cycloaddition for the Assembly of Atropoenantiomeric 3-Arylindolizines

Cited by 19 publications

References 56 publications

Synthesis of Axially Chiral Aldehydes by N‐Heterocyclic‐Carbene‐Catalyzed Desymmetrization Followed by Kinetic Resolution

Synthesis of Axially Chiral Aldehydes by N‐Heterocyclic‐Carbene‐Catalyzed Desymmetrization Followed by Kinetic Resolution

Advances in Atroposelectively De Novo Synthesis of Axially Chiral Heterobiaryl Scaffolds

Chiral Phosphoric Acid-Catalyzed Asymmetric Arylation of Indolizines: Atroposelective Access to Axially Chiral 3-Arylindolizines

Contact Info

Product

Resources

About