Construction of axial chirality via palladium/chiral norbornene cooperative catalysis

Liu, Ze‐Shui; Yu, Hao; Gao, Qianwen; Ma, Yuanyuan; Tang, Hua; Shang, Yongjia; Cheng, Hong‐Gang; Zhou, Qianghui

doi:10.1038/s41929-020-0494-1

Cited by 124 publications

(71 citation statements)

References 40 publications

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“…5 ). Inspired by recent studies on Pd/chiral norbornene asymmetric catalysis 65 – 67 , we tested the synthesis of axially chiral 2-pyridone using enantiopure (+)- N 9 (99% ee ) 66 , 67 as the mediator and sterically demanding 2,6-disubstituted aryl bromide 2L as the arylating reagent. Pleasingly, the desired product 4A* was obtained in 73% yield and excellent enantiomeric excess (97% ee ), after minor modification of the reaction conditions (Table 4C and see Supplementary Table 8 for details).…”

Section: Resultsmentioning

confidence: 99%

Diversity-oriented functionalization of 2-pyridones and uracils

Shang¹,

Gao³

et al. 2021

Nat Commun

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Heterocycles 2-pyridone and uracil are privileged pharmacophores. Diversity-oriented synthesis of their derivatives is in urgent need in medicinal chemistry. Herein, we report a palladium/norbornene cooperative catalysis enabled dual-functionalization of iodinated 2-pyridones and uracils. The success of this research depends on the use of two unique norbornene derivatives as the mediator. Readily available alkyl halides/tosylates and aryl bromides are utilized as ortho-alkylating and -arylating reagents, respectively. Widely accessible ipso-terminating reagents, including H/DCO2Na, boronic acid/ester, terminal alkene and alkyne are compatible with this protocol. Thus, a large number of valuable 2-pyridone derivatives, including deuterium/CD3-labeled 2-pyridones, bicyclic 2-pyridones, 2-pyridone-fenofibrate conjugate, axially chiral 2-pyridone (97% ee), as well as uracil and thymine derivatives, can be quickly prepared in a predictable manner (79 examples reported), which will be very useful in new drug discovery.

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Section: Resultsmentioning

confidence: 99%

Diversity-oriented functionalization of 2-pyridones and uracils

Shang¹,

Gao³

et al. 2021

Nat Commun

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“…Very recently, Zhou and co‐workers constructed the axially chiral scaffold 52 by employing such a reaction with chiral norbornene (Scheme 24b). [ 64 ] Aryl iodides and 2,6‐substituted aryl bromides served as the substrate and arylation reagent, respectively, and a variety of axially chiral biaryls were obtained by intermolecular termination. It's worth noting that if an ortho ‐acetyl group existed in the aryl bromides, chiral fluorenols were generated through an axial‐to‐central chirality transfer process.…”

Section: Typical Catellani Reactionsmentioning

confidence: 99%

Catellani Reaction: An Enabling Technology for Vicinal Functionalization of Aryl Halides by Palladium(0)/Norbornene Cooperative Catalysis

Dong

Luan

2021

Chin. J. Chem.

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The Catellani reaction, originally discovered by Catellani in 1997, and further developed by Catellani, Lautens and others, has emerged as a powerful strategy for the synthesis of polysubstituted arenes, which would be difficult to access via traditional methods. In this process, both ortho-and ipso-positions of aryl halides could be functionalized simultaneously with different electrophiles and terminating agents under the cooperative catalysis of palladium and norbornene (NBE). This review focuses on the significant progress of such transformations, and the section of typical Catellani reactions is divided into five parts according to the functionalization mode of ortho-C-H bond: alkylation, arylation, amination, acylation or thiolation.

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“…However, owing to multiple formidable challenges, [16] it has rarely been realized so far [17] . Recently, we developed an efficient method to access axially chiral biaryls via Pd 0 /chiral NBE* cooperative catalysis [17c] . Inspired by this chemistry, we envisioned a strategy for KR of tertiary benzyl alcohols.…”

Section: Figurementioning

confidence: 99%

“…Nevertheless, multiple challanges are foreseeable. For example, the identification of a suitable chiral NBE* co‐catalyst to ensure both good reactivity and enantiodiscrimination, [16] the innate low reactivity of 2,6‐disubstituted arylbromide motif of the tertiary alcohols, [17c] and the dichotomy between required high reaction temperature and expected good KR effciency.…”

Section: Figurementioning

confidence: 99%

Kinetic Resolution of Tertiary Benzyl Alcohols via Palladium/Chiral Norbornene Cooperative Catalysis

Liu

Xie

et al. 2021

Angewandte Chemie

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Herein we report a highly enantioselective kinetic resolution of tertiary benzyl alcohols via palladium/chiral norbornene cooperative catalysis. With simple aryl iodides as the resolution reagent, a wide range of readily available racemic tertiary benzyl alcohols are applicable to this method. Both chiral tertiary benzyl alcohols and benzo[c]chromene products are obtained in good to excellent enantioselectivities (selectivity factor up to 544). The appealing synthetic utility of the obtained enantioenriched tertiary alcohols is demonstrated by the facile preparation of several valuable chiral heterocycles. Preliminary mechanism studies include DFT calculations to explain the origin of enantiodiscrimination and control experiments to uncover the formation of a transient axial chirality during the kinetic resolution step.

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Construction of axial chirality via palladium/chiral norbornene cooperative catalysis

Cited by 124 publications

References 40 publications

Diversity-oriented functionalization of 2-pyridones and uracils

Diversity-oriented functionalization of 2-pyridones and uracils

Catellani Reaction: An Enabling Technology for Vicinal Functionalization of Aryl Halides by Palladium(0)/Norbornene Cooperative Catalysis

Kinetic Resolution of Tertiary Benzyl Alcohols via Palladium/Chiral Norbornene Cooperative Catalysis

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