ChemInform Abstract: Enantioselective Steglich Rearrangement of Oxindole Derivatives by Easily Accessible Chiral N,N‐4‐(Dimethylamino)pyridine Derivatives.

Mandai, Hiroki; Fujiwara, Takuma; Noda, Katsuaki; Fujii, Kazuki; Mitsudo, Koichi; Korenaga, Takashi; Suga, Seiji

doi:10.1002/chin.201605134

Cited by 2 publications

(2 citation statements)

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“…In 2015, Suga and co-workers developed a series of new C-3 functionalized DAMP-type catalysts readily prepared by the Ugi multicomponent reaction in a one-pot style (Scheme 5). 25 The easily accessible chiral nucleophilic catalysts C1 and C2 have been efficiently applied to the enantioselective Steglich rearrangement of oxindole derivatives 10 to give the corresponding products 11 bearing an all-carbon quaternary center with excellent yields and enantioselectivities (up to >98% yield, 99 : 1 er).…”

Section: Nucleophilic Catalysismentioning

confidence: 99%

Recent advances in catalytic asymmetric [1,3]-rearrangement reactions

Zhang

Chen

2022

Org. Chem. Front.

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Section: Nucleophilic Catalysismentioning

confidence: 99%

Recent advances in catalytic asymmetric [1,3]-rearrangement reactions

Zhang

Chen

2022

Org. Chem. Front.

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“…Initial catalyst attack forms an ion pair between the acylated catalyst and the enolate species in a stepwise fashion. The formation of this complex was also invoked in a recent computational study of the Steglich rearrangement of oxindole derivatives by Suga 39 and is supported by X-ray crystal structures. 40 Regiodivergence occurs through preferential attack on the acylated catalyst by the enolate at C4 or N1.…”

Section: Transition State Stabilizationmentioning

confidence: 99%

Computational Insights into the Central Role of Nonbonding Interactions in Modern Covalent Organocatalysis

et al. 2016

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The flexibility, complexity, and size of contemporary organocatalytic transformations pose interesting and powerful opportunities to computational and experimental chemists alike. In this Account, we disclose our recent computational investigations of three branches of organocatalysis in which nonbonding interactions, such as C-H···O/N interactions, play a crucial role in the organization of transition states, catalysis, and selectivity. We begin with two examples of N-heterocyclic carbene (NHC) catalysis, both collaborations with the Scheidt laboratory at Northwestern. In the first example, we discuss the discovery of an unusual diverging mechanism in a catalytic kinetic resolution of a dynamic racemate that depends on the stereochemistry of the product being formed. Specifically, the major product is formed through a concerted asynchronous [2 + 2] aldol-lactonization, while the minor products come from a stepwise spiro-lactonization pathway. Stereoselectivity and catalysis are the results of electrophilic activation from C-H···O interactions between the catalyst and the substrate and conjugative stabilization of the electrophile. In the second example, we show how knowledge and understanding of the computed transition states led to the development of a more enantioselective NHC catalyst for the butyrolactonization of acyl phosphonates. The identification of mutually exclusive C-H···O interactions in the computed major and minor TSs directly resulted in structural hypotheses that would lead to targeted destabilization of the minor TS, leading to enhanced stereoinduction. Synthesis and evaluation of the newly designed NHC catalyst validated our hypotheses. Next, we discuss two works related to Lewis base catalysis involving 4-dimethylaminopyridine (DMAP) and its derivatives. In the first, we discuss our collaboration with the Smith laboratory at St Andrews, in which we discovered the origins of the regioselectivity in carboxyl transfer reactions. We disclose how different Lewis base catalysts (NHC or DMAP) can lead to different regiomeric products as a result of differing magnitudes of aromatic and C-H···O interactions present in the respective transition states. In the second example, we discuss the mechanism and origins of the stereoselectivity of a reaction catalyzed by a planar-chiral 4-(pyrrolidino)pyridine derivative, namely, the coupling of ketenes with cyanopyrrole. We discovered that the chiral base mechanism is operative, in contrast to the originally proposed Brønsted acid mechanism. The selectivity is determined by the ease with which the major and minor TSs can realize strong stabilizing C-H···N interactions between the pyrrole cyano group and the catalyst. These interactions induce increased catalyst distortion in the minor TS, thereby leading to enantioselectivity. Finally, we discuss our computations related to amine-based organocatalysis in collaboration with the Carter laboratory at Oregon State. We probed the mechanism and stereoselectivity of a bifunctional amine thiourea-catalyzed Michael rea...

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ChemInform Abstract: Enantioselective Steglich Rearrangement of Oxindole Derivatives by Easily Accessible Chiral N,N‐4‐(Dimethylamino)pyridine Derivatives.

Cited by 2 publications

References 1 publication

Recent advances in catalytic asymmetric [1,3]-rearrangement reactions

Recent advances in catalytic asymmetric [1,3]-rearrangement reactions

Computational Insights into the Central Role of Nonbonding Interactions in Modern Covalent Organocatalysis

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