Light‐Mediated Aminocatalysis: The Dual‐Catalytic Ability Enabling New Enantioselective Route

Roy, Sourav; Paul, Hrishikesh; Chatterjee, Indranil

doi:10.1002/ejoc.202200446

Cited by 11 publications

(4 citation statements)

References 115 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, the photochemistry of organocatalytic intermediates can open up new synthetic possibilities, expanding the scope of organocatalysis to encompass radical chemistry and excited-state reactivity. 116,117 In addition, integrating the photochemical activity of chiral organocatalytic intermediates within metal-mediated catalytic cycles may also enable unconventional mechanisms for stereocontrolled bond formation. 118 6.3.…”

Section: Stereochemistry and Isomerizationmentioning

confidence: 99%

“…New research findings have also shown that by using light to excite chiral organocatalytic intermediates, novel catalytic functions can be activated, thus enabling the synthesis of chiral molecules that would otherwise be challenging to obtain using conventional ground-state reactivity. Therefore, the photochemistry of organocatalytic intermediates can open up new synthetic possibilities, expanding the scope of organocatalysis to encompass radical chemistry and excited-state reactivity. , In addition, integrating the photochemical activity of chiral organocatalytic intermediates within metal-mediated catalytic cycles may also enable unconventional mechanisms for stereocontrolled bond formation …”

Section: Hit-to-lead and Lead Optimizationmentioning

confidence: 99%

See 1 more Smart Citation

Photochemistry in Medicinal Chemistry and Chemical Biology

Zhu,

Empel,

Pelliccia

et al. 2024

J. Med. Chem.

View full text Add to dashboard Cite

Photochemistry has emerged as a transformative force in organic chemistry, significantly expanding the chemical space accessible for medicinal chemistry. Light-induced reactions enable the efficient synthesis of intricate organic structures and have found applications throughout the different stages of the drug discovery and development processes. Moreover, photochemical techniques provide innovative solutions in chemical biology, allowing precise spatiotemporal drug activation and targeted delivery. In this Perspective, we highlight the already numerous remarkable applications and the even more promising future of photochemistry in medicinal chemistry and chemical biology. ■ SIGNIFICANCE• Medicinal chemistry and chemical biology can highly benefit from the recent developments in the field of photochemistry in organic synthesis. • The most relevant applications of photochemistry and photocatalysis in the different stages of the drug discovery process have been highlighted. • With this Perspective, we would like to point out the potential and challenges of photochemistry in chemical biology applications.

show abstract

Section: Stereochemistry and Isomerizationmentioning

confidence: 99%

Section: Hit-to-lead and Lead Optimizationmentioning

confidence: 99%

Photochemistry in Medicinal Chemistry and Chemical Biology

Zhu,

Empel,

Pelliccia

et al. 2024

J. Med. Chem.

View full text Add to dashboard Cite

show abstract

“…While the enamine activation mode has proved quite successful for the enantioselective α-functionalization of linear aldehydes [ 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 ], its extension to α-branched aldehydes progresses with paucity. In response to this situation, complementary activation modes have entered the field, including methods based on dual activation strategies [ 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ]. In 2014, Moreau and coworkers published a major review entitled asymmetric organocatalytic functionalization of α,α-disubstituted aldehydes through enamine activation [ 35 ].…”

Section: Introductionmentioning

confidence: 99%

Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes

et al. 2023

View full text Add to dashboard Cite

Aldehydes constitute a main class of organic compounds widely applied in synthesis. As such, catalyst-controlled enantioselective α-functionalization of aldehydes has attracted great interest over the years. In this context, α-branched aldehydes are especially challenging substrates because of reactivity and selectivity issues. Firstly, the transient trisubstituted enamines and enolates resulting upon treatment with an aminocatalyst or a base, respectively, would exhibit attenuated reactivity; secondly, mixtures of E- and Z-configured enamines/enolates may be formed; and third, effective face-discrimination on such trisubstituted sp2 carbon intermediates by the incoming electrophilic reagent is not trivial. Despite these issues, in the last 15 years, several catalytic approaches for the α-functionalization of prostereogenic α-branched aldehydes that proceed in useful yields and diastereo- and enantioselectivity have been uncovered. Developments include both organocatalytic and metal-catalyzed approaches as well as dual catalysis strategies for forging new carbon–carbon and carbon–heteroatom (C-O, N, S, F, Cl, Br, …) bond formation at Cα of the starting aldehyde. In this review, some key early contributions to the field are presented, but focus is on the most recent methods, mainly covering the literature from year 2014 onward.

show abstract

“…Recent elegant examples of photochemical enantioselective α-functionalizations of carbonyl compounds have been developed with alkyl halides. 3–6 Notably, Melchiorre and co-workers pioneered the use of α-bromoketones and benzylic bromides as alkylating agents via light activated charge-transfer complexes. 5 We were interested in developing a complementary approach for the catalytic enantioselective α-alkylation of aldehydes 1 based on renewable and sustainable sources of alkylating reagents.…”

Section: Introductionmentioning

confidence: 99%