Practical Synthesis of Optically Active Styrene Oxides via Reductive Transformation of 2-Chloroacetophenones with Chiral Rhodium Catalysts

Hamada, Takayuki; Torii, Takayoshi; Izawa, Kunisuke; Noyori, Ryoji; Ikariya, Takao

doi:10.1021/ol020213o

Cited by 118 publications

(43 citation statements)

References 27 publications

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“…[10] Facile access to enantiopure halohydrins is achieved via catalytic asymmetric reduction of the corresponding a-halo-ketones via chiral organo catalysts [10,11] or biocatalysts. For the biocatalytic approach, the following systems were employed: (i) isolated alcohol dehydrogenases (e.g., from Rhodococcus erythropolis, [12] bakers yeast, [13 -15] horse liver, Thermoanaerobium brockii, Lactobacillus brevis, [16] or Pseudomonas sp.…”

Section: Introductionmentioning

confidence: 99%

“…One reason for the high significance of chiral a-halohydrins is their broad applicability as chiral intermediates, e.g,. a-halohydrins can easily be converted to the corresponding chiral epoxides, [11,30,33] which opens a large spectrum for further transformations. We present here an asymmetric reduction by biocatalytic hydrogen transfer of a-halo-ketones to access for some substrates both enantiomers of chiral halohydrins and a novel "one-pot one-step" cascade-reaction consisting of a biocatalytic reduction of a-halo ketones and in situ base-induced ring closure to furnish the corresponding epoxide.…”

Section: Introductionmentioning

confidence: 99%

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Non‐Racemic Halohydrins via Biocatalytic Hydrogen‐Transfer Reduction of Halo‐Ketones and One‐Pot Cascade Reaction to Enantiopure Epoxides

et al. 2005

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Biocatalytic hydrogen-transfer reduction of a-chloro-ketones furnished non-racemic chlorohydrins by employing either Rhodococcus ruber as lyophilized cell catalyst or an alcohol dehydrogenase preparation from Pseudomonas fluorescens DSM 50106 (PF-ADH). For all substrates investigated, Rhodococcus ruber gave strictly the "Prelog" product, whereas PF-ADH showed scattered stereopreference. One possibility for a follow-up reaction of halohydrins is the ring closure to the corresponding epoxide.A novel "one pot-one step strategy" was employed to obtain the enantiopure epoxide from the a-chloro-ketone in a cascade like fashion at pH > 12 involving biocatalytic hydrogen transfer reduction and in situ chemo-catalyzed ring closure.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Non‐Racemic Halohydrins via Biocatalytic Hydrogen‐Transfer Reduction of Halo‐Ketones and One‐Pot Cascade Reaction to Enantiopure Epoxides

et al. 2005

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“…A variety of ring-substituted ¡-chloroacetophenones is also reducible with a chiral Cp*Rh complex, [Cp*RhCl{(R,R)-Tsdpen}], to provide quantitatively chiral alcohols with an excellent ee. 17 A more appealing feature is that one-pot synthesis of a chiral styrene oxide can be performed by sequential asymmetric reduction of chloroacetophenone with the chiral Rh in 2-propanol followed by treatment of the reaction mixture with NaOH aqueous solution, leading to the desired products in an isolated yield of 8090% with 96 98% ee in a single reactor (Figure 4). 18 For example, (S)-mchlorostyrene oxide, which is a key intermediate for the preparation of several ¢3-adrenergic receptor agonist compounds, is easily obtained through this the one-pot procedure.…”

Section: Asymmetric Transfer Hydrogenation Of C=o and C=n Double Bondmentioning

confidence: 99%

Chemistry of Concerto Molecular Catalysis Based on the Metal/NH Bifunctionality

Ikariya¹

2010

Bulletin of the Chemical Society of Japan

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125

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The development of conceptually new bifunctional transition-metal-based catalysts for a wide range of catalytic reactions is described. The bifunctional chiral molecular catalyst based on metalligand cooperation was originally developed for asymmetric transfer hydrogenation of ketones and imines and is now applicable to chemo-and stereoselective reductive and oxidative transformations as well as to enantioselective CC and CN bond formations with a wide scope and high practicability. The structural modification and electronic fine-tuning of the protic amine chelating ligands are crucial to develop unprecedented catalytic reactions. Cp*Ru complexes bearing a diamine (NN) or aminophosphine (PN) ligand readily activate H 2 , and can effect hydrogenation of polar functionalities. The bifunctional Ir complexes promote aerobic oxidative transformation of alcohols into ketones and esters and are applicable to kinetic resolution of racemic secondary alcohols. A novel imido-bridged dirhodium complex, which is a dinuclear variant of the bifunctional mononuclear amido complexes, promotes aerobic oxidation of a secondary alcohol and H 2 . In addition, the metal/NH bifunctional property also affects efficiently enantioselective conjugate additions. The present concerto molecular catalysts offer a great opportunity to open up new fundamentals for stereoselective molecular transformations.

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“…Most of the compounds listed in Tables 1-5 (24-91 except 33, 45-53, 84, 90), were prepared by nucleophilic addition of alkyl amines bearing various heterocycles, tryptophan derivatives, or tryptamine derivatives to the racemic 3-chlorostyrene oxide (9) or its optical isomer 25,[52][53][54][55][56][57] (R)-9 in MeOH (Chart 6, method X).…”

Section: Chemistrymentioning

confidence: 99%

Discovery of a Novel and Potent Human and Rat .BETA.3-Adrenergic Receptor Agonist, [3-[(2R)-[[(2R)-(3-Chlorophenyl)-2-hydroxyethyl]amino]propyl]-1H-indol-7-yloxy]acetic Acid

Harada

Hirokawa

Suzuki

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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1) This sub-classification has led to the development of b 1 -and b 2 -AR antagonists and/or agonists which have been useful for the treatment of cardiovascular diseases and asthma. In early 1980s, a third b-AR, initially referred to as "atypical"2) and later called b 3 -AR has been found in a number of species, including man, [3][4][5][6] and in 1989, the human, 7) rat, 8) and mouse 9) b 3 -ARs were first cloned and characterized. Like other b-ARs, b 3 -ARs belong to the G-protein-coupled receptor family that includes receptors with a common structure consisting of seven transmembrance-spanning connected by interhelical loops.10) The b 3 -AR is located on the surface of both white and brown adipocytes and is known to be stimulated by endogenous catecholamines, adrenalin, and noradrenaline. It has also been reported that b 3 -AR receptor plays a significant role in regulating lipolysis and thermogenesis in rodent and human adipose tissues. 11,12) Moreover, studies of b 3 -AR mRNA demonstrated that, b 3 -ARs exist in human heart, gall bladder, gastrointestinal tract, prostate, and urinary bladder detrusor tissue in addition to adipocytes. [13][14][15][16] Since the discovery of b 3 -AR, a number of laboratories have been engaged in developing potent and selective b 3 -AR agonists for the treatment of various metabolic and gastrointestinal diseases such as obesity, non-insulin dependent (Type-II) diabetes, irritable bowel syndrome, and urinary frequency and incontinence. [17][18][19][20][21] Early b 3 -AR agonists (the "first generation" of potent and selective rat b 3 -AR agonists) such as BRL 37344 (BRL 35135), [22][23][24] CL 316243, [25][26][27] and SR 58611A, 28) having a 3-chlorophenyl moiety in the left-hand side (LHS) and a carboxylic acid or an ester functionality in the right-hand side (RHS) as shown in Chart 1, have been reported to be effective anti-obesity and anti-diabetic agents in rodents.29) These compounds, through their potent agonistic activity for the b 3 -AR, stimulate lipolysis and energy expenditure and cause only a slight increase in heart rate (b 1 -AR activity) and weak muscle tremor (b 2 -AR activity). Unfortunately, some of these early b 3 -AR agonists developed for the treatment of metabolic disorders failed to produce similar effects in humans, due to a lack of selectivity and/or potency, or poor pharmacokinetics.30) Because of structural differences between human and rat b 3 -ARs with regard to the amino acid sequences of each receptor, activity at the rat b 3 -AR could not effectively predict that at the human b 3 -AR.31) Thus, a new generation of human b 3 -AR agonists with minimal side effects associated with activation of human b 1 -and b 2 -ARs has long been needed.A new generation of b 3 -AR agonists currently under preclinical development is represented by the tetrahydroisoquinoline 1, [32][33][34] SB 226552, 35,36) L 755507, 37) L 770644, 38,39) and LY-377604 40) (Chart 1). These compounds having both potent and full agonistic activity, and high selectivity at the human b...

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Practical Synthesis of Optically Active Styrene Oxides via Reductive Transformation of 2-Chloroacetophenones with Chiral Rhodium Catalysts

Cited by 118 publications

References 27 publications

Non‐Racemic Halohydrins via Biocatalytic Hydrogen‐Transfer Reduction of Halo‐Ketones and One‐Pot Cascade Reaction to Enantiopure Epoxides

Non‐Racemic Halohydrins via Biocatalytic Hydrogen‐Transfer Reduction of Halo‐Ketones and One‐Pot Cascade Reaction to Enantiopure Epoxides

Chemistry of Concerto Molecular Catalysis Based on the Metal/NH Bifunctionality

Discovery of a Novel and Potent Human and Rat .BETA.3-Adrenergic Receptor Agonist, [3-[(2R)-[[(2R)-(3-Chlorophenyl)-2-hydroxyethyl]amino]propyl]-1H-indol-7-yloxy]acetic Acid

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