A new enzymatic approach to (R)-Tamsulosin hydrochloride

Acetti, Daniela; Brenna, Elisabetta; Fuganti, Claudio

doi:10.1016/j.tetasy.2007.01.012

Cited by 16 publications

(9 citation statements)

References 10 publications

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“…As a result, tamsulosin 6.2 was obtained in 27% yield in the form of hydrochloride (21% RME, 2.3 g of the product was obtained). 246 Enantioselective reductive amination was implemented in the synthesis of tamsulosin proposed by Maeda from Hamari Chemicals (Scheme 113). 247 The authors condensed amine 6.2.c and ketone 6.2.d to produce a Schiff base.…”

Section: Tamsulosinmentioning

confidence: 99%

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Reductive Amination in the Synthesis of Pharmaceuticals

et al. 2019

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Reductive amination plays a paramount role in pharmaceutical and medicinal chemistry owing to its synthetic merits and the ubiquitous presence of amines among biologically active compounds. It is one of the key approaches to C–N bond construction due to its operational easiness and a wide toolbox of protocols. Recent studies show that at least a quarter of C–N bond-forming reactions in the pharmaceutical industry are performed via reductive amination. This Review concisely compiles information on 71 medical substances that are synthesized by reductive amination. Compounds are grouped according to the principle of action, which includes drugs affecting the central nervous system, drugs affecting the cardiovascular system, anticancer drugs, antibiotics, antiviral and antifungal medicines, drugs affecting the urinary system, drugs affecting the respiratory system, antidiabetic medications, drugs affecting the gastrointestinal tract, and drugs regulating metabolic processes. A general synthetic scheme is provided for each compound, and the description is focused on reductive amination steps. The green chemistry metric of reaction mass efficiency was calculated for all reactions.

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Section: Tamsulosinmentioning

confidence: 99%

“…Brenna et al carried out the synthesis of enantiomerically pure azide 6.2.a and conducted its reduction with subsequent reductive alkylation by aldehyde 6.2.b (Scheme ). As a result, tamsulosin 6.2 was obtained in 27% yield in the form of hydrochloride (21% RME, 2.3 g of the product was obtained) …”

Section: Drugs Affecting the Urinary Genital Systemmentioning

confidence: 99%

Reductive Amination in the Synthesis of Pharmaceuticals

et al. 2019

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“…These compounds are commonly synthesized by alkylation of phenols with 2-halo amines [1,4] or of amines with 2-aryloxyethyl halides [4]. Also, reductive amination of aryloxyacetaldehydes with the use of sodium tetrahydridoborate [2,3,5] or hydrogen over Pd/C [6] was reported. However, the yields are not high, and they rarely exceed 50%.…”

mentioning

confidence: 99%

Synthesis of aryloxyacetaldehydes and N-(aryloxyethyl)cyclohexanamine hydrochloroides

2010

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Oxidation of 2-(aryloxymethyl)oxiranes with periodic acid gave a series of aryloxyacetaldehydes which reacted with cyclohexylamine in THF, and subsequent reduction of Schiff bases thus obtained with sodium tetrahydridoborate resulted in the formation of the corresponding secondary amines which were isolated and characterized as hydrochlorides.Aryloxyethanamines are known to exhibit biological activity. In particular, compounds acting as local anesthetics, adrenergic neuron blocking agents [1, 2], and dopamine D 2 -receptor inhibitors [3] were found among aryloxyethanamine derivatives. These compounds are commonly synthesized by alkylation of phenols with 2-halo amines [1,4] or of amines with 2-aryloxyethyl halides [4]. Also, reductive amination of aryloxyacetaldehydes with the use of sodium tetrahydridoborate [2, 3, 5] or hydrogen over Pd/C [6] was reported. However, the yields are not high, and they rarely exceed 50%. For example, Sakurai et al. [3] described the reaction of substituted phenoxyacetaldehydes with primary and secondary amine hydrochlorides in methanol in the presence of triethylamine, followed by reduction with NaBH 4 , which afforded 11-31% of the corresponding 2-phenoxyethanamines.Aryloxyacetaldehydes necessary for the synthesis of aryloxyethanamines according to [3] can also be prepared in several ways: by catalytic oxidation of 2-phenoxyethanol [7], by alkylation of phenols with bromoacetaldehyde acetals and subsequent hydrolysis [2,8], by ozonolysis of allyl phenyl ethers [9], and by oxidation of glycerol monophenyl ether with lead tetraacetate [10]. The most appropriate procedure seems to be oxidation of 2-(aryloxymethyl)oxiranes with periodic acid in aqueous medium or aqueous dioxane, which was proposed in [11] for the synthesis of phenoxyacetaldehyde.In the present article we report on the synthesis of 2-(aryloxymethyl)oxiranes and their oxidation with periodic acid to obtain aryloxyacetaldehydes. The latter were converted into the corresponding N-cyclohexyl imines which were reduced to amines with sodium tetrahydridoborate. N-(Aryloxyethyl)cyclohexanamines were isolated and characterized as hydrochlorides.By heating substituted phenols with excess 2-(chloromethyl)oxirane in aqueous sodium hydroxide we obtained the corresponding 2-(aryloxymethyl)-

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“…For products 5a , 5c , 5d , 5e , 5g , and 5h configuration was assigned by comparison of the sign of optical rotation with that described in the literature. For compounds 5b , 5f , 5i , and 5j configuration was assigned by analogy with the previous data.…”

Section: Methodsmentioning

confidence: 99%

Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters

et al. 2017

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The catalytic asymmetric hydrogenation of trisubstituted enol esters using Rh catalysts bearing chiral phosphine-phosphite ligands (P-OP) has been studied. Substrates covered comprise α,β-dialkyl, α-alkyl-β-aryl, and α,β-diarylvinyl esters, the corresponding hydrogenation products being suitable precursors to prepare synthetically relevant chiral nonfunctionalized alcohols. A comparison of reactivity indicates that it decreases in the order: α,β-dialkyl > α-alkyl-β-aryl > α,β-diaryl. Based on the highly modular structure of P-OP ligands employed, catalyst screening identified highly enantioselective catalysts for α,β-dialkyl (95-99% ee) and nearly all of α-alkyl-β-aryl substrates (92-98% ee), with the exception of α-cyclohexyl-β-phenylvinyl acetate which exhibited a low enantioselectivity (47% ee). Finally, α,β-diarylvinyl substrates showed somewhat lower enantioselectivities (79-92% ee). In addition, some of the catalysts provided a high enantioselectivity in the hydrogenation of E/Z mixtures (ca. Z/E = 75:25) of α,β-dialkylvinyl substrates, while a dramatic decrease on enantioselectivity was observed in the case of α-methyl-β-anisylvinyl acetate (Z/E = 58:42). Complementary deuteration reactions are in accord with a highly enantioselective hydrogenation for both olefin isomers in the case of α,β-dialkylvinyl esters. In contrast, deuteration shows a complex behavior for α-methyl-β-anisylvinyl acetate derived from the participation of the E isomer in the reaction.

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A new enzymatic approach to (R)-Tamsulosin hydrochloride

Cited by 16 publications

References 10 publications

Reductive Amination in the Synthesis of Pharmaceuticals

Reductive Amination in the Synthesis of Pharmaceuticals

Synthesis of aryloxyacetaldehydes and N-(aryloxyethyl)cyclohexanamine hydrochloroides

Broad Scope Synthesis of Ester Precursors of Nonfunctionalized Chiral Alcohols Based on the Asymmetric Hydrogenation of α,β-Dialkyl-, α,β-Diaryl-, and α-Alkyl-β-aryl-vinyl Esters

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