Asymmetric Intramolecular Hydroalkylation of Internal Olefin with Cycloalkanone to Directly Access Polycyclic Systems

Wang, Aifang; Tian, Jin‐Miao; Zhao, Xiaojing; Li, Zi-Hao; Zhang, Ye; Lu, Ka; Wang, Hong; Zhang, Shuyu; Tu, Yong‐Qiang; Ding, Tong‐Mei; Xie, Yuyang

doi:10.1002/anie.202308858

Cited by 4 publications

(3 citation statements)

References 80 publications

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“…Besides pyrazoleamide 1a , other β,γ-unsaturated amides were examined . The use of amide 1b provided a better chemical yield and enantioselectivity than amide 1a (entry 15 vs entry 12), so amide 1b was selected as the pronucleophile for further study.…”

Section: Resultsmentioning

confidence: 99%

Cu-Catalyzed Direct Enantioselective Vinylogous Mannich Reaction between β,γ-Unsaturated Pyrazoleamides and Ketimines

Luo,

Hou,

et al. 2024

J. Org. Chem.

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A catalytic asymmetric vinylogous Mannich-type reaction between β,γ-unsaturated amides and ketimines has been developed in excellent regio-, diastereo-, and enantioselectivities. The methodology provides an efficient approach to construct chiral homoallylic amines with a 3-amino-2-oxindole scaffold. Moreover, the transformations of the chiral products, including the removal of the pyrazole group or Boc group, the reduction of the C−C double bond, and Suzuki coupling, have been investigated.

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Section: Resultsmentioning

confidence: 99%

Cu-Catalyzed Direct Enantioselective Vinylogous Mannich Reaction between β,γ-Unsaturated Pyrazoleamides and Ketimines

Luo,

Hou,

et al. 2024

J. Org. Chem.

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“…Functional groups containing oxygen and nitrogen were both well-tolerated (25)(26)(27)(28)(29). In addition, chlorine, iodine, ester, azide and amide groups were also accommodated (27)(28)(29)(30)(31)(32)(33)(34)(35). Subsequently, we turned our attention to N-Boc-protected amino acid substrates.…”

Section: Substrate Scopementioning

confidence: 99%

“…Over the past few years, various directing groups (DG) have been employed to facilitate difunctionalization of unactivated alkenes, which have made considerable progress [30][31][32][33][34][35] . To the best of our knowledge, intermolecular metal-catalyzed remote allylic C-H oxidation of internal alkenes by DG has not been previously reported.…”

mentioning

confidence: 99%

Cooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline

Wang,

et al. 2024

Nat Commun

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Aliphatic allylic amines are common in natural products and pharmaceuticals. The oxidative intermolecular amination of C(sp3)-H bonds represents one of the most straightforward strategies to construct these motifs. However, the utilization of widely internal alkenes with amines in this transformation remains a synthetic challenge due to the inefficient coordination of metals to internal alkenes and excessive coordination with aliphatic and aromatic amines, resulting in decreasing the reactivity of the catalyst. Here, we present a regioselective Cu-catalyzed oxidative allylic C(sp3)-H amination of internal olefins with azodiformates to these problems. A removable bidentate directing group is used to control the regiochemistry and stabilize the π-allyl-metal intermediate. Noteworthy is the dual role of azodiformates as both a nitrogen source and an electrophilic oxidant for the allylic C-H activation. This protocol features simple conditions, remarkable scope and functional group tolerance as evidenced by >40 examples and exhibits high regioselectivity and excellent E/Z selectivity.

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Olefination of Aromatic Carbonyls via Site‐Specific Activation of Cycloalkanone Ketals**

To,

Nguyen

2023

Angewandte Chemie

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Skeletal editing is an important strategy in organic synthesis as it modifies the carbon backbone to tailor molecular structures with precision, enabling access to compounds with specific desired properties. Skeletal editing empowers chemists to transform synthetic approaches of target compounds across diverse applications from drug discovery to materials science. Herein, we introduce a new skeletal editing method to convert readily available aromatic carbonyl compounds into valuable unsaturated carboxylic acids with extended carbon chains. Our reaction setup enables a cascade reaction of enolization‐[2+2]cycloaddition‐[2+2]cycloreversion between aromatic carbonyl compounds and ketals of cyclic ketones to generate unsaturated carboxylic acids as ring‐opening products. Through a simple design, our substrates are specifically activated to react at predetermined positions to enhance selectivity and efficiency. This practical method offers convenient access to versatile organic building blocks as well as provides fresh insights into manipulating traditional reaction pathways for new synthetic applications.

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Asymmetric Intramolecular Hydroalkylation of Internal Olefin with Cycloalkanone to Directly Access Polycyclic Systems

Cited by 4 publications

References 80 publications

Cu-Catalyzed Direct Enantioselective Vinylogous Mannich Reaction between β,γ-Unsaturated Pyrazoleamides and Ketimines

Cu-Catalyzed Direct Enantioselective Vinylogous Mannich Reaction between β,γ-Unsaturated Pyrazoleamides and Ketimines

Cooperative Cu/azodiformate system-catalyzed allylic C–H amination of unactivated internal alkenes directed by aminoquinoline

Olefination of Aromatic Carbonyls via Site‐Specific Activation of Cycloalkanone Ketals**

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