Substituted Isoquinolines by Noyori Transfer Hydrogenation:  Enantioselective Synthesis of Chiral Diamines Containing an Aniline Subunit

Vedejs, E.; Trapencieris, Pēteris; Sūna, Edgars

doi:10.1021/jo990594s

Cited by 106 publications

(59 citation statements)

References 9 publications

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“…In some early examples, Vedejs et al used a Noyori catalyst to synthesize new asymmetric proton donors [188] and Sheldon and coworkers produced a key intermediate in the synthesis of morphine [189]. A group of researchers at Glaxo Wellcome published the syntheses of the neuromuscular blocker GW0430 and related compounds using transfer hydrogenation as a key step [190,191].…”

Section: Syntheses Using the Asymmetric Transfer Hydrogenation Of Imimentioning

confidence: 99%

Chiral Amines from Transition‐Metal‐Mediated Hydrogenation and Transfer Hydrogenation

Church¹,

Andersson²

2010

Chiral Amine Synthesis

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This chapter focuses specifically on the synthesis of amines of the form HNR Ã R 1 , NR Ã R 1 R 2 , and HN(X)R Ã (R Ã ¼ chiral alkyl group; R 1 , R 2 ¼ alkyl or aryl groups; X ¼ heteroatom such as N, S, or P) via the asymmetric hydrogenation of imines, enamines, and iminiums. Thus, we will discuss the formation of amines that have (i) chirality a to the nitrogen, and (ii) no carbonyl group a to nitrogen. Many reported examples of this reaction use substrates with C¼N moieties in a ring, so cyclic amines will receive considerable attention. We will discuss in detail the formation of chiral amines using the asymmetric reduction of aza-aromatic substrates, which has been a popular topic in recent years, and will cover the use of N-carbonyl groups to facilitate this reaction. However, the hydrogenations of nonaromatic a,b-unsaturated amides will not be discussed. Though chiral amides (HN(R Ã )C(O)R 1 ) can be produced highly enantioselectively using these reactions, the sheer number of publications on the topic places it outside the scope of this chapter. These hydrogenations are, however, well covered in a number of existing books and review articles [1]. In addition, we will not cover the related process, reductive amination, which is discussed elsewhere in this book.6.2 Chiral Amines with a Disubstituted Nitrogen Atom, HNR Ã R 1 Direct Asymmetric Hydrogenation of Alkyl-and Aryl-Substituted IminesThough less developed than the analogous reductions of olefins and ketones, the iridium-catalyzed asymmetric hydrogenation of imines (especially N-benzyl and Naryl amines) has received considerable study. It has therefore been the subject of

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Section: Syntheses Using the Asymmetric Transfer Hydrogenation Of Imimentioning

confidence: 99%

Chiral Amines from Transition‐Metal‐Mediated Hydrogenation and Transfer Hydrogenation

Church¹,

Andersson²

2010

Chiral Amine Synthesis

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“…In some early work, Vedejs was able to obtain some excellent results through reaction optimization but also found that the reaction was highly dependent on the structure of the substrate (Scheme 11.12 ) [43] . The desired product of Vedejs ' study was the ortho -amino -substituted (20) , for use as a chiral hydrogen donor.…”

Section: Tetrahydroisoquinolines and Tetrahydro -B -Carbolinesmentioning

confidence: 99%

Imino Reductions by Transfer Hydrogenation

Wills

2008

Modern Reduction Methods

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11 History and BackgroundIn contrast to ketones, and in particular with respect to asymmetric reductions, the reduction of compounds containing C = N bonds has remained relatively underdeveloped. Some signifi cant breakthroughs have, however, been reported in the last ten years. This chapter will review reductions through metal hydride complexes, " Meerwein -Ponndorf -Verley ( MPV ) type " reductions, and other methods including transfer hydrogenation with organocatalysts and asymmetric LeuckartWallach aminations of ketones. Although there will be discussion of mechanistic aspects, the main focus of this review will be on more recent synthetic applications. The reader ' s attention is also directed to a number of recent useful reviews of this area [1] . Mechanisms of C= N Bond Reduction by Transfer HydrogenationUsing either organic or organometallic catalysts, transfer hydrogenation of imines and other C = N bond -containing substrates, is most commonly carried out using isopropanol, formic acid or a formate salt as the hydrogen source. The most commonly, but not exclusively, used metals are ruthenium, rhodium and iridium.The mechanism of the transfer hydrogenation of imines has been the subject of some extended synthetic, computational and mechanistic studies. The tutorial review by B ä ckvall [1f] provides a very good summary of this. An excellent review by Morris [1c] also contains an incisive overview of hydrogenation and transfer hydrogenation and provides a very logical nomenclature for the possible reduction reaction pathway.The mechanisms that may be considered for imine reduction are the same as for ketone reductions and may be divided into two broad classes (Figure 11.1 ). In the fi rst of these, the MPV reduction or its reverse (Oppenauer oxidation), a metal

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“…Transfer hydrogenation using stable organic hydrogen donors such as 2-propanol or formic acid is an attractive solution to the above demand. Some recent examples include tetrahydroisoquinolines (13) [47,48] and indole alkaloids (14)(15)(16) [49]. The methodology has been applied to a numerous synthesis of optically active amines.…”

Section: Transfer Hydrogenationmentioning

confidence: 99%

Recent Advances in Catalytic Asymmetric Addition to Imines and Related C=N Systems

Vilaivan¹,

Bhanthumnavin²,

Sritana-anant

2005

COC

150

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Addition reactions to imines are relatively less developed compared to those of carbonyl compounds due to low electrophilicity and ease of α-deprotonation. With the use of an appropriate activator, which can coordinate to the imine nitrogen atom, the electrophilicity of the imine can be enhanced and a range of nucleophilic addition reactions becomes possible. When the activator is chiral, it will also create chiral environment and will direct the approach of the nucleophile to one face of the imine over the other resulting in enantioselectivity. The potential of catalytic asymmetric addition to imines in organic synthesis is enormous, but is relatively underused. With the development of many highly effective chiral catalysts for imine additions, the situation will soon be changed. The present review will cover selected literature on catalytic asymmetric additions to aldimines, ketimines and related compounds including hydrazones, oximes and nitrones from 1999 to 2004. The reactions of interest include hydrogenation, alkylation, Mannich and related reactions such as aza-Baylis-Hillman and aza-Henry reaction, Strecker reaction, hydrophosphonylation, and 3-6 membered ring forming reactions from imines. Some applications of these methodologies in synthesis of nitrogen-containing biologically active compounds will also be presented.

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Substituted Isoquinolines by Noyori Transfer Hydrogenation: Enantioselective Synthesis of Chiral Diamines Containing an Aniline Subunit

Cited by 106 publications

References 9 publications

Chiral Amines from Transition‐Metal‐Mediated Hydrogenation and Transfer Hydrogenation

Chiral Amines from Transition‐Metal‐Mediated Hydrogenation and Transfer Hydrogenation

Imino Reductions by Transfer Hydrogenation

Recent Advances in Catalytic Asymmetric Addition to Imines and Related C=N Systems

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