Synergistic Strategies in Aminocatalysis

Vecchio, Antonio Del; Sinibaldi, Arianna; Nori, Valeria; Giorgianni, Giuliana; Carmine, Graziano Di; Pesciaioli, Fabio

doi:10.1002/chem.202200818

Cited by 19 publications

(12 citation statements)

References 198 publications

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“…[73][74][75][76][77][78][79][80][81][82][83][84][85] Particularly, in recent years, the combination of organocatalysis and transition metal catalysis or the synergy of organocatalysis and photocatalysis or electrocatalysis has been demonstrated as an efficient fashion to realize a series of enantio-selective CDC reactions, expanding the scope and potential of this field. [70][71][72][86][87][88][89][90][91][92][93][94][95][96][97][98] Two comprehensive reviews were published seven years ago on the topic of C-H functionalization through organocatalysis. 70,71 However, there is no reviews focusing on organocatalytic CDC reactions despite its significance.…”

Section: Jie Luomentioning

confidence: 99%

“…73–85 Particularly, in recent years, the combination of organocatalysis and transition metal catalysis or the synergy of organocatalysis and photocatalysis or electrocatalysis has been demonstrated as an efficient fashion to realize a series of enantioselective CDC reactions, expanding the scope and potential of this field. 70–72,86–98…”

Section: Introductionmentioning

confidence: 99%

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Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Jiang,

Luo,

Zhao

2024

Green Chem.

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Section: Jie Luomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Jiang,

Luo,

Zhao

2024

Green Chem.

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“…Both secondary and primary aminocatalysts have been widely examined and have proved to be viable for synergistic catalysis. 20,21 However, a single type of aminocatalyst able to incorporate all different synergistic strategies is still very rare. Previously, we reported chiral primary−tertiary vicinal diamines as a functional and mechanistic mimic of Type I aldolase.…”

Section: Introductionmentioning

confidence: 99%

“…Particularly, the acid–base, redox, and excited-state properties can be fine-tuned to achieve uncharted reactivity beyond the reach of aminocatalysis only. Both secondary and primary aminocatalysts have been widely examined and have proved to be viable for synergistic catalysis. , However, a single type of aminocatalyst able to incorporate all different synergistic strategies is still very rare. Previously, we reported chiral primary–tertiary vicinal diamines as a functional and mechanistic mimic of Type I aldolase. , In the past few years, we have endeavored much effort in exploring primary amine-based synergistic catalysis. , One type of vicinal chiral primary–tertiary diamine catalyst has been found to work synergistically or cooperatively with a number of transition metal catalysts, such as Pd, Rh, Ag, Co, and Cu; as well as other organocatalysts, such as B(C 6 F 5 ) 3 , ketone, selenium, and iodide; photocatalysis; and electrochemical processes.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Transformations by “1 + x” Synergistic Catalysis with Chiral Primary Amines

Cai,

Zhang,

Zhang

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Synergistic catalysis is a powerful tool that involves two or more distinctive catalytic systems to activate reaction partners simultaneously, thereby expanding the reactivity space of individual catalysis. As an established catalytic strategy, organocatalysis has found numerous applications in enantioselective transformations under rather mild conditions.Recently, the introduction of other catalytic systems has significantly expanded the reaction space of typical organocatalysis. In this regard, aminocatalysis is a prototypical example of synergistic catalysis. The combination of aminocatalyst and transition metal could be traced back to the early days of organocatalysis and has now been well explored as an enabling catalytic strategy. Particularly, the acid−base properties of aminocatalysis can be significantly expanded to include usually electrophiles generated in situ via metal-catalyzed cycles. Later on, aminocatalyst has also been exploited in synergistically combining with photochemical and electrochemical processes to facilitate redox transformations. However, synergistically combining one type of aminocatalyst with many different catalytic systems remains a great challenge. One of the most daunting challenges is the compatibility of aminocatalysts in coexistence with other catalytic species. As nucleophilic species, aminocatalysts may also bind with metal, which leads to mutual inhibition or even quenching of the individual catalytic activity. In addition, oxidative stability of aminocatalyst is also a nonneglectable issue, which causes difficulties in exploring oxidative enamine transformations.In 2007, we developed a vicinal diamine type of chiral primary aminocatalysts. This class of primary aminocatalysts was developed and evolved as functional and mechanistic mimics to the natural aldolase and has been widely applied in a number of enamine/ iminium ion-based transformations. By following a "1 + x" synergistic strategy, the chiral primary amine catalysts were found to work synergistically or cooperatively with a number of transition metal catalysts, such as Pd, Rh, Ag, Co, and Cu, or other organocatalysts, such as B(C 6 F 5 ) 3 , ketone, selenium, and iodide. Photocatalysis and electrochemical processes can also be incorporated to work together with the chiral primary amine catalysts. The 1 + x catalytic strategy enabled us to execute unexploited transformations by fine-tuning the acid−base and redox properties of the enamine intermediates and to achieve effective reaction and stereocontrol beyond the reach individually. During these efforts, an unprecedented excited-state chemistry of enamine was uncovered to make possible an effective deracemization process. In this Account, we describe our recent efforts since 2015 in exploring synergistic chiral primary amine catalysis, and the content is categorized according to the type of synergistic partner such that in each section the developed synergistic catalysis, reaction scopes, and mechanistic features...

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“…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

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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.

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Synergistic Strategies in Aminocatalysis

Cited by 19 publications

References 198 publications

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Enantioselective cross-dehydrogenative coupling enabled by organocatalysis

Enantioselective Transformations by “1 + x” Synergistic Catalysis with Chiral Primary Amines

Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes

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