En Route to an Efficient Catalytic Asymmetric Synthesis of AS-3201

Mashiko, Tomoyuki; Hara, Kenshiro; Tanaka, Daisuke; Fujiwara, Yuji; Kumagai, Naoya; Shibasaki, Masakatsu

doi:10.1021/ja0752585

Cited by 122 publications

(49 citation statements)

References 24 publications

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“…Early in 2007, Shibasaki et al devised an elegant asymmetric lanthanum-catalyzed amination occurring between cyclic imide 191 and di-t-butylazodicarboxylate 192 to give the corresponding product 193 that was directly deprotected by treatment with HCl gas bubbling into toluene to provide final hydrazine 194 in 96% yield and 91% ee [100]. The latter constituted a key intermediate in the total synthesis of aldose reductase inhibitor AS-3201.…”

Section: Miscellaneous Enantioselective Lanthanide-catalyzed Reactionsmentioning

confidence: 99%

Recent developments in enantioselective lanthanide-catalyzed transformations

Pellissier

2017

Coordination Chemistry Reviews

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Section: Miscellaneous Enantioselective Lanthanide-catalyzed Reactionsmentioning

confidence: 99%

Recent developments in enantioselective lanthanide-catalyzed transformations

Pellissier

2017

Coordination Chemistry Reviews

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“…Exploration of the catalysts prepared from a combination of RE metals/amide-based ligands 28,29) showed that the amide-based ligand (R)-4a was a promising chiral ligand for catalytic asymmetric amination of 3. 30) The synthesis of bis(2-hydroxyphenyl)amide (R)-4a is straightforward and easy to prepare in large quantities from commercially available N-tert-butoxycarbonyl (Boc)-D-valine without using column chromatography. The first-generation amination catalyst, prepared by mixing (R)-4a and La(O i Pr) 3 in a 2 : 1 ratio, promoted the asymmetric amination of 3 and di-tert-butyl azodicarboxylate in CHCl 3 in the presence of N,N-dimethylacetamide, affording the desired amination product 5 in Ͼ99% yield and 92% ee (Chart 2).…”

Section: Catalytic Asymmetric Amination Of Succinimide Derivatives mentioning

confidence: 99%

Development of Atom-Economical Catalytic Asymmetric Reactions under Proton Transfer Conditions: Construction of Tetrasubstituted Stereogenic Centers and Their Application to Therapeutics

Kumagai

2011

CHEMICAL & PHARMACEUTICAL BULLETIN

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The development of atom-economical catalytic asymmetric reactions based on two distinct sets of catalyst, a rare earth metal/amide-based ligand catalyst and a soft Lewis acid/hard Brønsted base catalyst, is reviewed. These catalytic systems exhibit high catalytic activity and stereoselectivity by harnessing a cooperative catalysis through hydrogen bond/metal coordination and soft-soft interactions/hard-hard interactions, respectively. The effectiveness of these cooperative catalysts is clearly delineated by the high stereoselectivity in reactions with highly coordinative substrates, and the specific activation of otherwise low-reactive pronucleophiles under proton transfer conditions. The rare earth metal/amide-based ligand catalyst was successfully applied to catalytic asymmetric aminations, nitroaldol (Henry) reactions, Mannich-type reactions, and conjugate addition reactions, generating stereogenic tetrasubstituted centers. Catalytic asymmetric amination and anti-selective catalytic asymmetric nitroaldol reactions were successfully applied to the efficient enantioselective synthesis of therapeutic candidates, such as AS-3201 and the b b 3 -adrenoreceptor agonist, showcasing the practical utility of the present protocols. The soft Lewis acid/hard Brønsted base cooperative catalyst was specifically developed for the chemoselective activation of soft Lewis basic allylic cyanides and thioamides, which are otherwise low-reactive pronucleophiles. The cooperative action of the catalyst allowed for efficient catalytic generation of active carbon nucleophiles in situ, which were integrated into subsequent enantioselective additions to carbonyl-type electrophiles.

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“…[8] Several asymmetric variants for the α-amination of carbonyl compounds have been reported. [9] The metalmediated enantioselective synthesis of α-hydrazino acids and α-amino acids has been demonstrated with 1,3-dicarbonyl compounds, [10] oxo esters [11] and metal enolates/silyl enols [12] as carbon nucleophiles. The use of electrophilic reagents such as dialkyl azodicarboxylates (DAADs) makes this synthetic approach more attractive.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient and Practical Pyrrolidine–Camphor‐Derived Organocatalysts for the Direct α‐Amination of Aldehydes

Liu¹,

Magar²,

Chen³

2010

Eur J Org Chem

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A series of pyrrolidine-camphor-derived organocatalysts (1-4) were designed and synthesised. These organocatalysts were used for direct α-amination of aldehydes with dialkyl azodicarboxylates to give the desired α-aminated products in high chemical yields (up to 92 %) and with high to excellent levels of stereoselectivity (up to Ͼ99 % ee). The reactions proceeded rapidly (within 5 min) with low catalyst loading (5 mol-%) at ambient temperature. Enantioselective aminations of asymmetric α,α-disubstituted aldehydes in the cata-

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En Route to an Efficient Catalytic Asymmetric Synthesis of AS-3201

Cited by 122 publications

References 24 publications

Recent developments in enantioselective lanthanide-catalyzed transformations

Recent developments in enantioselective lanthanide-catalyzed transformations

Development of Atom-Economical Catalytic Asymmetric Reactions under Proton Transfer Conditions: Construction of Tetrasubstituted Stereogenic Centers and Their Application to Therapeutics

Highly Efficient and Practical Pyrrolidine–Camphor‐Derived Organocatalysts for the Direct α‐Amination of Aldehydes

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