Asymmetric reactions catalyzed by chiral metal complexes. 41. Highly efficient asymmetric hydrogenation of amino ketone derivatives leading to practical syntheses of (S)-propranolol and related compounds

Takahashi, Hisashi; Sakuraba, Shunji; Takeda, Hideo; Achiwa, Kazuo

doi:10.1021/ja00171a036

Cited by 114 publications

(23 citation statements)

References 1 publication

(2 reference statements)

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“…[22]. Although this may not be seen as a shortfall today, derivatives (18) of BPPM have been developed, mainly through different nitrogen substituents, and derivatives such as PPPM (18c) still give d-amino acids [85,[87][88][89][90][91][92][93][94][95][96][97][98]. The ligands are also useful for the reduction of itaconic acid derivatives [3].…”

Section: Diop 749mentioning

confidence: 99%

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

Ager¹

2006

The Handbook of Homogeneous Hydrogenation

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23Enantioselective Alkene Hydrogenation: Introduction and Historic Overview Development of CAMP and DIPAMPDuring the late 1960s, Horner et al. [13] and Knowles and Sabacky [14] independently found that a chiral monodentate tertiary phosphine, in the presence of a rhodium complex, could provide enantioselective induction for a hydrogenation, although the amount of induction was small [15][16][17][18][19][20]. The chiral phosphine ligand replaced the triphenylphosphine in a Wilkinson-type catalyst [10,21,22]. At about this time, it was also found that [Rh(COD) 2 ] + or [Rh(NBD) 2 ] + could be used as catalyst precursors, without the need to perform ligand exchange reactions [23].Knowles found that the monophosphine CAMP (1a) could provide an ee-value of up to 88% for the reduction of dehydroamino acids. CAMP was an extension of PAMP (1b) that provides ee-values of 50-60% in analogous reactions [24]. At this time, Kagan showed that DIOP (2) (vide infra), where the stereogenic centers are not at phosphorus, could also provide enantioselective induction in an hydrogenation. DIOP also showed that a bisphosphine need not have the chirality at phosphorus, and that good stereoselectivity might result from a C 2 -symmetric ligand. Knowles then developed the C 2 -symmetric ligand DIPAMP (3) [22,25]. The use of Rh-DIPAMP for the synthesis of l-Dopa is well known and is still practiced today [12,22,27]. A number of variations of the DIPAMP structure were investigated for the synthesis of this important pharmaceutical, but the parent remains the best ligand in this class [22].

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Section: Diop 749mentioning

confidence: 99%

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

Ager¹

2006

The Handbook of Homogeneous Hydrogenation

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“…One such example is the synthesis of ethyl (R)-2-hydroxy-4-phenylbutyrate, an important intermediate for the angiotensinconverting enzyme (ACE) inhibitor benazepril, or for coenzyme A, using the NORPHOS ligand (Scheme 33.9) [21].…”

Section: A-ketoesters and Ketoamidesmentioning

confidence: 99%

“…The rhodium precatalysts, when combined with chiral phosphorus ligands such as BPPFOH 4 [20 b], hydroxyproline derivatives ligands [20][21][22][23][24], Cy,Cy-oxo-ProNOP 15, Cp,Cp-oxoProNOP 16, and The reactions were conducted to completion after 5 to 24 h. Cp,Cp-IndoNOP 18 [15 p], have provided excellent enantioselectivity and reactivity for the enantioselective hydrogenation of a-, b-, and c-alkyl amino ketone hydrochloride salts.…”

Section: A-amino Ketonesmentioning

confidence: 99%

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Rhodium‐Catalyzed Enantioselective Hydrogenation of Functionalized Ketones

Mortreux¹,

Karim²

2006

The Handbook of Homogeneous Hydrogenation

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This chapter is dedicated to the memory of Professors Francis Petit and Hidemasa Takaya, two friends who have been pioneers in the field of homogeneous catalysis and enantioselective catalysis. IntroductionEnantioselective hydrogenation, using molecular hydrogen to reduce prochiral olefins, ketones, and imines, has become one of the most efficient, practical, and atom-economical methods for the construction of chiral compounds [1-3]. Since the early 1970s, significant attention has been devoted to the discovery of new asymmetric catalysts, in which transition metal complexes modified by chiral phosphorous ligands have emerged as preferential catalysts for asymmetric hydrogenation. Thousands of efficient chiral phosphorous ligands with diverse structures have been developed for their application to asymmetric hydrogenation. Indeed, many represent the key step in industrial processes for the preparation of enantiomerically pure compounds. Consequently, numerous reviews have been devoted to the application of enantioselective catalysis in that context [4, 5].In this chapter, we will focus on the rhodium-catalyzed hydrogenation of functionalized ketones and the development of chiral phosphorous ligands for this process. Although there are other chiral phosphorous ligands which are effective for ruthenium-, iridium-, platinum-, titanium-, zirconium-, and palladium-catalyzed hydrogenation, they will not be discussed here. For details of these chemistries, the reader should refer to other chapters of this book.

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“…There are only a few reports in literature about the synthesis of Mephenoxalone. [10][11][12][13] Previously, we reported the synthesis of a bronchodilator blocker Fenspiride (5) 14 and continuing our interest in cyclization reactions using bistrichloromethyl carbonate (BTC or triphosgene) and the addition of trimethylsilyl cyanide to aldehydes, 15 we proposed a new methodology for the synthesis of Mephenoxalone through silanized intermediate.…”

Section: Introductionmentioning

confidence: 99%

New synthesis of mephenoxalone

Ochoa-Terán¹,

Rivero²

2008

Arkivoc

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Mephenoxalone (1) was synthesized through a silanizated intermediate prepared from the addition of trimethylsilyl cyanide (TMSCN) to (o-methoxy)phenoxyacetaldehyde (10). Three different methods were established to synthesize this aldehyde. Alkylation of guaiacol with bromoacetaldehyde diethyl acetal, followed by acid hydrolysis of acetal group gave the highest overall yield (49%) for the aldehyde 10. Different reagents as ZnI 2 , Montmorillonite K10, (+)-Eu(tfc) 3 and (+)-Yb(tfc) 3 were used in the addition of TMSCN to the aldehyde giving very good yields with all catalysts.

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Asymmetric reactions catalyzed by chiral metal complexes. 41. Highly efficient asymmetric hydrogenation of amino ketone derivatives leading to practical syntheses of (S)-propranolol and related compounds

Cited by 114 publications

References 1 publication

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

Enantioselective Alkene Hydrogenation: Introduction and Historic Overview

Rhodium‐Catalyzed Enantioselective Hydrogenation of Functionalized Ketones

New synthesis of mephenoxalone

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