Enantioselective Synthesis of Isatin‐Derived α‐(Trifluoromethyl)imine Derivatives: Phosphine‐Catalyzed γ‐Addition of α‐(Trifluoromethyl)imines and Allenoates

Gao, Yafei; Shi, Min

doi:10.1002/ejoc.201700048

Cited by 26 publications

(11 citation statements)

References 112 publications

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“…Using isatin-derived α -(trifluoromethyl)imines as pronucleophiles, Shi and co-workers also achieved enantioselective umpolung γ -additions to allenoates (Scheme 141). 216 In the presence of the thiourea-derived bifunctional chiral phosphine P39 (20 mol %), a series of isatin-derived α -(trifluoromethyl)imines reacted efficiently with various allenoates to afford their corresponding isatin-derived α -(trifluoromethyl)imine derivatives in good to excellent yields and with moderate to good enantioselectivities.…”

Section: Nucleophilic Phosphine Catalysis Of Allenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Nucleophilic Phosphine Catalysis Of Allenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…Nucleophilic phosphines, known as Lewis base catalysts, have attracted more and more attention due to the advantages of high efficiency, versatility, and easy operation . Particularly, the nucleophilic phosphine catalyzed annulation reaction is one of the most powerful synthesis methods to afford a wide range of carbocyclic and heterocyclic compound . Since the pioneering work on the phosphine‐catalyzed [3 + 2] annulation reaction of unsubstituted allenoates, numerous annulation reactions of allenoates involving using phosphine as the catalyst have been developed …”

Section: Introductionmentioning

confidence: 99%

Mechanisms of phosphine‐catalyzed [4 + 3] annulation of allenoates with C, N‐cyclic azomethine imines: A DFT investigation

Zhu

Guo

et al. 2018

Int J of Quantum Chemistry

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In this article, mechanisms of phosphine‐catalyzed [4 + 3] annulation of allenoates with C, N‐cyclic azomethine imines have been investigated using density functional theory. The catalytic cycle for the title reaction consists of five steps. Namely, the first step is the nucleophilic addition of phosphine catalyst, the second one is the CC bond formation, the third one is the proton transfer process, and the next one is the ring‐closure process, the last one is dissociation of the catalyst and the product generation. The calculated results indicate that the nucleophilic addition of phosphine catalyst is rate‐determining. With the use of Cat as the chiral catalyst, optically active products were obtained in good yields with excellent enantioselectivities while the CC bond formation is stereoselectivity‐determining. Furthermore, the theoretically predicted the main product is SS configuration, which is in good agreement with the experimental results. The special role of the catalysts and origin of stereoselectivity was also identified by NBO, GRI, and FMO analyses. This work might be helpful for understanding the significant roles of phosphine catalyst and thus provide valuable insights on the rational design of potential catalysts for this kind of reactions.

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“…As a result, the unsaturated amines bear only one stereogenic center. , The same class of nucleophiles have been utilized in a γ-selective allylation with Morita–Baylis–Hillman-type allylic carbonates by employing a chiral nucleophilic catalyst (Scheme ). These coupling processes can yield homoallylic amines with vicinal syn stereogenic centers; however, the product scope is limited to aryl-substituted allylic centers and carbonyl-containing alkenes. , …”

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confidence: 99%

Enantio- and Diastereoselective Synthesis of Homoallylic α-Trifluoromethyl Amines by Catalytic Hydroalkylation of Dienes

2020

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We describe a strategy for the enantio-and diastereoselective synthesis of homoallylic α-trifluoromethyl amines by the catalytic hydroalkylation of terminal dienes. Trifluoromethylsubstituted isatin-derived azadienolate nucleophiles undergo γ-selective alkylation with a Pd-DTBM-SEGPHOS catalyst, which additionally promotes regioselective addition to the diene and delivers products in up to 86% yield, 10:1 dr, and 97.5:2.5 er.

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Enantioselective Synthesis of Isatin‐Derived α‐(Trifluoromethyl)imine Derivatives: Phosphine‐Catalyzed γ‐Addition of α‐(Trifluoromethyl)imines and Allenoates

Cited by 26 publications

References 112 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Mechanisms of phosphine‐catalyzed [4 + 3] annulation of allenoates with C, N‐cyclic azomethine imines: A DFT investigation

Enantio- and Diastereoselective Synthesis of Homoallylic α-Trifluoromethyl Amines by Catalytic Hydroalkylation of Dienes

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