Asymmetric hydrogenation with a complex of rhodium and a chiral bisphosphine

Knowles, William S.; Sabacky, M. J.; Vineyard, B. D.; Weinkauff, D. J.

doi:10.1021/ja00842a058

Cited by 430 publications

(166 citation statements)

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“…Some prominent examples of chiral bidentate phosphines include Kagan's DIOP [2], Knowles' DIPAMP [3], or Noyori's BINAP [4 -8], all of which became key components of many transition metal catalysts that are now widely used in organic and organometallic chemistry. Chirality is introduced into the structure of these ligands in several ways, viz.…”

Section: Introductionmentioning

confidence: 99%

“…Chirality is introduced into the structure of these ligands in several ways, viz. by inserting a chiral backbone [2, 4 -8], introducing P-centered chirality [3], or attaching readily available chiral ancillary substituents as e. g. in bidentate bis-phosphetanes [9,10] or bis-phospholanes [11 -16], respectively. Although many commonly applied ligands stand out by their C 2 -symmetrical molecular structures, which were long thought to have a beneficial effect on asymmetric induction [17], it has recently been pointed out that C 1 -symmetric ligands may provide similar or even superior enantiocontrol [18].…”

Section: Introductionmentioning

confidence: 99%

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On the Synthesis and Addition Reactions of Chiral N-Heterocyclic Diphosphines

Förstera

Hartenbach

Nieger

et al. 2012

Zeitschrift Für Naturforschung B

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Reaction of chiral N-heterocyclic chlorophosphines with lithium diphenylphosphide or of achiral N-heterocyclic chlorophosphines with optically active lithium menthyl phosphide produces chiral N-heterocyclic diphosphines which can be utilized in subsequent diphosphination reactions with activated alkenes or alkynes. The reaction with alkynes proceeds stereospecifically to produce Zethylene-1,2-bisphosphines which are readily converted to nickel(II) or palladium(II) complexes. Reactions with alkenes are synthetically less useful as the addition proceeds without any chiral induction at the newly formed stereocenters to yield inseparable mixtures of diastereomeric products. The molecular structures of chiral Z-ethylene-1,2-bisphosphine complexes and of a chiral N-heterocyclic chlorophosphine have been determined by single-crystal X-ray diffraction.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

On the Synthesis and Addition Reactions of Chiral N-Heterocyclic Diphosphines

Förstera

Hartenbach

Nieger

et al. 2012

Zeitschrift Für Naturforschung B

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“…Its high capacity for asymmetric induction, up to 88%, was demonstrated in the hydrogenation of -dehydroamino acids and enamides [5], and these excellent results stimulated the design and synthesis of many other C2-symmetric phosphine ligands. The most notable ligand reported in the period up to 1979 was 1,2-bis(o-anisylphenylphosphino)ethane (DIPAMP) developed by Knowles (Nobel laureate in 2001) et al at Monsanto in 1975, which provided very high enantioselectivity values up to 96% in the hydrogenation of -dehydroamino acids [6]. The methodology was used to produce (S)-3-(3,4-dihydroxyphenyl)alanine (L-DOPA), which is useful in the treatment of Parkinson's disease.…”

Section: Scheme 2 First Example Of Homogeneous Asymmetric Hydrogenationmentioning

confidence: 99%

Asymmetric Hydrogenation

2011

Homogeneous Catalysts

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“…Knowles liderou o desenvolvimento deste projeto, onde o aminoácido desejado foi obtido com elevados excessos enantioméricos (ee), por meio de uma reação catalítica assimétrica de hidrogenação de um alceno utilizando como ligante uma fosfina quiral, (R,R)-DIPAMP (Esquema 1). 9 Da mesma forma, diversas classes de fármacos puderam ou ainda serão beneficiadas pelos avanços da catálise assimétrica. Dentre as já beneficiadas citam-se: anti-inflamatórios não esteroidais, beta-bloqueadores, agentes anti-hipertensivos, antibióticos, antidepressivos, anticonvulsivantes, antivirais, anti-hipercolesterolemicos, antiparkinsonianos, etc.…”

Section: Introductionunclassified

Catálise assimétrica no Brasil: desenvolvimento e potencialidades para o avanço da indústria química brasileira

Braga¹,

Lüdtke²,

Schneider³

et al. 2013

Quím. Nova

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Recebido em 11/7/13; aceito em 9/10/13; publicado na web em 24/10/13 ASYMMETRIC CATALYSIS IN BRAZIL: DEVELOPMENT AND POTENTIAL FOR ADVANCEMENT OF BRAZILIAN CHEMICAL INDUSTRY. The preparation of enantiomerically pure or enriched substances is of fundamental importance to pharmaceutical, food, agrochemical, and cosmetics industries and involves a growing market of hundreds of billions of dollars. However, most chemical processes used for their production are not environmentally friendly because in most cases, stoichiometric amounts of chiral inductors are used and substantial waste is produced. In this context, asymmetric catalysis has emerged as an efficient tool for the synthesis of enantiomerically enriched compounds using chiral catalysts. More specifically, considering the current scenario in the Brazilian chemical industry, especially that of pharmaceuticals, the immediate prospect for the use of synthetic routes developed in Brazil in an enantioselective fashion or even the discovery of new drugs is practically null. Currently, the industrial production of drugs in Brazil is primarily focused on the production of generic drugs and is basically supported by imports of intermediates from China and India. In order to change this panorama and move forward toward the gradual incorporation of genuinely Brazilian synthetic routes, strong incentive policies, especially those related to continuous funding, will be needed. These incentives could be a breakthrough once we establish several research groups working in the area of organic synthesis and on the development and application of chiral organocatalysts and ligands in asymmetric catalysis, thus contributing to boost the development of the Brazilian chemical industry. Considering these circumstances, Brazil can benefit from this opportunity because we have a wide biodiversity and a large pool of natural resources that can be used as starting materials for the production of new chiral catalysts and are creating competence in asymmetric catalysis and related areas. This may decisively contribute to the growth of chemistry in our country.Keywords: asymmetric catalysis; chiral compounds; chiral catalyst. INTRODUÇÃOCom o objetivo de fomentar e contribuir na formulação de novas políticas de C&T, especialmente para a área de Química, apresentam--se, nesse artigo, diagnósticos, reflexões e discussões sobre a atual situação da área de Catálise Assimétrica no Brasil. Propõem-se, ainda, ações que permitam à Química do País contribuir para um futuro próspero, seguro e sustentável para sua população. A presente proposta está de acordo com os position papers "Química sem Fronteiras" da Química Nova, 1 nos temas centrais: Indústria Química e Inovação, nos setores farmoquímicos, agroquímicos e de alimentos. Enquadra-se, também, nos temas transversais, nos setores de inovação e agregação de valores.Durante as últimas décadas grandes esforços vêm sendo realizados no sentido de se estabelecer rotas enantiosseletivas para a preparação de substâncias enantiomericamente puras ou enriq...

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Asymmetric hydrogenation with a complex of rhodium and a chiral bisphosphine

Cited by 430 publications

References 0 publications

On the Synthesis and Addition Reactions of Chiral N-Heterocyclic Diphosphines

On the Synthesis and Addition Reactions of Chiral N-Heterocyclic Diphosphines

Asymmetric Hydrogenation

Catálise assimétrica no Brasil: desenvolvimento e potencialidades para o avanço da indústria química brasileira

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