Cu(I)-Catalyzed Asymmetric α-Allenylation of Activated Ketimines with 3-Butynoates

Ran, Guang‐Yao; Chen, Chen; Yang, Xing‐Xing; Zhao, Zhi Gang; Du, Wei; Chen, Ying‐Chun

doi:10.1021/acs.orglett.0c01534

Cited by 26 publications

(12 citation statements)

References 53 publications

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“…In 2020, Du, Chen, and coworkers reported Cu(I)-catalyzed asymmetric α-allenylation of activated ketimines with 3-butynoates (Scheme 42) [128]. Screening of catalysts and reaction conditions was conducted with isatin-derived ketimines.…”

Section: Allenyl Copper Speciesmentioning

confidence: 99%

Asymmetric Catalytic Ketimine Mannich Reactions and Related Transformations

Reep

Jarvis

et al. 2021

Catalysts

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The catalytic enantioselective ketimine Mannich and its related reactions provide direct access to chiral building blocks bearing an α-tertiary amine stereogenic center, a ubiquitous structural motif in nature. Although ketimines are often viewed as challenging electrophiles, various approaches/strategies to circumvent or overcome the adverse properties of ketimines have been developed for these transformations. This review showcases the selected examples that highlight the benefits and utilities of various ketimines and remaining challenges associated with them in the context of Mannich, allylation, and aza-Morita–Baylis–Hillman reactions as well as their variants.

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Section: Allenyl Copper Speciesmentioning

confidence: 99%

Asymmetric Catalytic Ketimine Mannich Reactions and Related Transformations

Reep

Jarvis

et al. 2021

Catalysts

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“…The tertiary amine of 35 provides an additional H-bonding interaction with the nucleophile. The reactions are exceptionally fast (10 min at 0 °C), and the yields and stereoselectivities are universally high …”

Section: Addition Of Carbon- and Heteroatom-based Nucleophiles To Tri...mentioning

confidence: 95%

Strategies for the Catalytic Enantioselective Synthesis of α-Trifluoromethyl Amines

Onyeagusi

Malcolmson

2020

ACS Catal.

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The exploitation of the α-trifluoromethylamino group as an amide surrogate in peptidomimetics and drug candidates has been on the rise. In a large number of these cases, this moiety bears stereochemistry with the stereochemical identity having important consequences on numerous molecular properties, such as the potency of the compound. Yet, the majority of stereoselective syntheses of α-CF 3 amines rely on diastereoselective couplings with chiral reagents. Concurrent with the rapid expansion of fluorine into pharmaceuticals has been the development of catalytic enantioselective means of preparing α-trifluoromethyl amines. In this work, we outline the strategies that have been employed for accessing these enantioenriched amines, including normal polarity approaches and several recent developments in imine umpolung transformations.

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“…For example, Enders group pioneered squaramide‐catalyzed enantioselective Strecker reaction of pyzazolin‐5‐one derived ketimines with trimethylsilyl cyanide toward chiral pyrazolone α‐aminonitriles [8] . Subsequently, a few organocatalytic or metal‐catalyzed versions of pyzazolin‐5‐one‐derived ketimines with various nucleophiles, such as naphthols, [9] 2,4‐dihydro‐3H‐pyrazol‐3‐one, [10] 1H‐indol‐4‐ols, [11] β‐ketoacids, [12] silyl enol ethers [13] and benzyl but‐3‐ynoates, [14] were reported. Despite these significant advances, asymmetric addition of arylboronic acids as aryl pronucleophiles to pyrazolinone ketimines remains unexplored so far, probably because of the lack of effective asymmetric catalytic system.…”

Section: Methodsmentioning

confidence: 99%

Pd‐Catalyzed Asymmetric Addition of Arylboronic Acids to Pyrazolinone Ketimines

et al. 2021

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An asymmetric addition of arylboronic acids to pyrazolinone ketimines is reported using palladium/chiral N,N′‐disulfonyl bisimidazoline (Bim) catalytic system, producing 25 examples of enantioenriched 4‐amino‐5‐pyrazolones bearing one quaternary carbon stereocenter with 60–91% yields and 81–98% ee. The reaction demonstrates remarkable compatibility regarding pyrazolinone ketimines and arylboronic acids, rendering an enantioselective access to chiral aza‐heterocycles bearing α‐tertiary amines.

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Cu(I)-Catalyzed Asymmetric α-Allenylation of Activated Ketimines with 3-Butynoates

Cited by 26 publications

References 53 publications

Asymmetric Catalytic Ketimine Mannich Reactions and Related Transformations

Asymmetric Catalytic Ketimine Mannich Reactions and Related Transformations

Strategies for the Catalytic Enantioselective Synthesis of α-Trifluoromethyl Amines

Pd‐Catalyzed Asymmetric Addition of Arylboronic Acids to Pyrazolinone Ketimines

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