Catalytic Enantioselective Addition to Imines

Kobayashi, Shū; Ishitani, Haruro

doi:10.1021/cr980414z

Cited by 1,550 publications

(521 citation statements)

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“…T he synthesis of ␣-chiral amines using the catalytic asymmetric addition of diorganozinc reagents has produced very exciting results in recent years (1)(2)(3). This very important subunit is commonly found in many pharmaceuticals and other biologically important compounds.…”

mentioning

confidence: 99%

Catalytic asymmetric addition of diorganozinc reagents to N -phosphinoylalkylimines

Côté

Boezio

Charette

2004

Proc. Natl. Acad. Sci. U.S.A.

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The synthesis of ␣-chiral amines bearing two alkyl groups has been hampered by the accessibility and stability of the alkylimine precursor. Herein, we report an efficient strategy to generate the alkyl-substituted imine in situ that is compatible with the MeDuPHOS monoxide⅐Cu(I) catalyzed addition of diorganozinc reagents. The sulfinic acid adduct of the imine is readily prepared by mixing diphenylphosphinic amide, the aldehyde, and sulfinic acid. The sulfinic acid adduct is generally isolated by filtration. The addition of diorganozinc reagents in the presence of Me-DuPHOS monoxide⅐Cu(I) and the in situ-generated imines affords the corresponding ␣-chiral amines in high yields and enantiomeric excesses.

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mentioning

confidence: 99%

Catalytic asymmetric addition of diorganozinc reagents to N -phosphinoylalkylimines

Côté

Boezio

Charette

2004

Proc. Natl. Acad. Sci. U.S.A.

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“…Usually, organotin reagents are of low nucleophilicity. Their reaction with electrophiles needs the promotion by Lewis acids [18]. In absence of a Lewis acid, which, for example, may also activate the stannane via a chloride bridge, the reactivity of the stannane towards the iminium salt obviously is low and does not lead to a smooth conversion.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-induced Asymmetric Addition of Organometallic Compounds to Imines

Allef

Kunz

2009

Zeitschrift Für Naturforschung B

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“…Because the reaction of HCN with the imine might compete with the desired reaction of TMSCN as the nucleophile, we expected that it would be important to keep the concentration of HCN low by the slow addition of HCN. Thus, using 20 mol% of TMSCN and slowly adding the HCN (120 mol%) in CH 2 Cl 2 (system 2), we obtained the products with results (Table 5, entries [14][15][16][17][18][19] comparable to that of the TMSCN-PhOH system (system 1). Optimization of the amount of TMSCN and the slow addition of HCN increases the potential for the application of this catalytic asymmetric reaction to a large-scale Strecker-type synthesis using HCN as a stoichiometric cyanide source.…”

Section: -3 Catalytic Enantioselective Strecker-type Reactionmentioning

confidence: 99%

“…15) There have been several noteworthy reports on the use of organometallic reagents, such as alkyllithiums, ketene silyl acetals, organoboronic acids, or allylstannanes. Moreover, a chiral rhodium-catalyzed highly enantioselective conjugate addition of organoboronic acids to nitroalkenes was recently reported.…”

Section: )mentioning

confidence: 99%

Multifunctional Asymmetric Catalysis.

Shibasaki

Kanai

2001

Chem. Pharm. Bull.

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Two types of general and practical enantioselective catalysts, namely, bimetallic complexes and Lewis acid-Lewis base bifunctional catalysts were developed based on the concept of multifunctional catalysis. In the first part of this review, the first example of a catalytic enatioselective nitro-Mannich reaction as well as a direct catalytic enantioselective aldol reaction of 2-hydroxyacetophenone using bimetallic complexes is discussed. The new complex, composed of ytterbium, potassium, and BINOL in a ratio of 1 : 1 : 3, promoted the nitro-Mannich reaction of nitromethane with up to 91% ee. On the other hand, second generation ALB catalyzed an enantioselective and diastereoselective nitro-Mannich reaction of nitroalkanes in up to 83% ee with a diastereomeric ratio up to 7 : 1. Moreover, the reaction of aldehydes with 2-hydroxyacetophenone in the presence of LLB, KHMDS, and H 2 O selectively gave the corresponding anti-a a,b b-dihydroxy ketones in up to 95% ee and, in the presence of the catalyst prepared from linked-BINOL and 2 eq of Et 2 Zn, selectively afforded the syn-a a,b b-dihydroxy ketones in up to 86% ee. In the second part, the development of new catalysts displaying a Lewis acidity and a Lewis basicity is described. The Lewis acid of the catalyst activates aldehydes, imines, acyl quinoliniums, and ketones. At the same time, the Lewis base activates the nucleophile (TMSCN). Catalysts of this type produced a highly enantioselective cyanation of these electrophiles. Application of the catalytic enantioselective cyanosilylation of aldehydes to a total synthesis of epothilones is also described.

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Catalytic Enantioselective Addition to Imines

Cited by 1,550 publications

References 234 publications

Catalytic asymmetric addition of diorganozinc reagents to N -phosphinoylalkylimines

Catalytic asymmetric addition of diorganozinc reagents to N -phosphinoylalkylimines

Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-induced Asymmetric Addition of Organometallic Compounds to Imines

Multifunctional Asymmetric Catalysis.

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