Asymmetric Hydroformylation

Claver, Carmen; Diéguez, Montserrat; Pàmies, Òscar; Castillón, Sergio

doi:10.1007/3418_016

Cited by 50 publications

(6 citation statements)

References 78 publications

(110 reference statements)

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“…Asymmetric hydroformylation (AHF) is well-recognized as a powerful synthetic tool to construct a large variety of enantiomerically enriched compounds. − However, rather than chiral diphosphines, diphosphonites, or diphosphites, the most promising ligands for asymmetric hydroformylation are hybrid systems, such as phosphine-phosphite, phosphine-phosphinite, and phosphine-phosphoramidite ligands . To date, acyclic olefins and vinyl aromatics have been extensively explored in the AHF with both Rh and Pt, whereas heterocyclic olefins, such as dihydrofurans and pyrrolines, are scarcely reported, although the corresponding aldehydes are important building blocks in organic synthesis and medicinal chemistry .…”

Section: Introductionmentioning

confidence: 99%

Highly Selective Asymmetric Rh-Catalyzed Hydroformylation of Heterocyclic Olefins

et al. 2012

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A small family of new chiral hybrid, diphosphorus ligands, consisting of phosphine-phosphoramidites L1 and L2 and phosphine-phosphonites L3a−c, was synthesized for the application in Rh-catalyzed asymmetric hydroformylation of heterocyclic olefins. High-pressure (HP)-NMR and HP-IR spectroscopy under 5−10 bar of syngas has been employed to characterize the corresponding catalyst resting state with each ligand. Indole-based ligands L1 and L2 led to selective ea coordination, while the xanthene derived system L3c gave predominant ee coordination. Application of the small bite-angle ligands L1 and L2 in the highly selective asymmetric hydroformylation (AHF) of the challenging substrate 2,3-dihydrofuran (1) yielded the 2-carbaldehyde (3) as the major regioisomer in up to 68% yield (with ligand L2) along with good ee's of up to 62%. This is the first example in which the asymmetric hydroformylation of 1 is both regio-and enantioselective for isomer 3. Interestingly, use of ligand L3c in the same reaction completely changed the regioselectivity to 3-carbaldehyde (4) with a remarkably high enantioselectivity of 91%. Ligand L3c also performs very well in the Rh-catalyzed asymmetric hydroformylation of other heterocyclic olefins. Highly enantioselective conversion of the notoriously difficult substrate 2,5-dihydrofuran (2) is achieved using the same catalyst, with up to 91% ee, concomitant with complete regioselectivity to the 3-carbaldehyde product (4) under mild reaction conditions. Interestingly, the Rh-catalyst derived from L3c is thus able to produce both enantiomers of 3-carbaldehyde 4, simply by changing the substrate from 1 to 2. Furthermore, 85% ee was obtained in the hydroformylation of N-acetyl-3-pyrroline (5) with exceptionally high regioselectivities for 3-carbaldehyde 8Ac (>99%). Similarly, an ee of 86% for derivative 8Boc was accomplished using the same catalyst system in the AHF of N-(tert-butoxycarbonyl)-3-pyrroline (6). These results represent the highest ee's reported to date in the AHF of dihydrofurans (1, 2) and 3-pyrrolines (5, 6).

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Section: Introductionmentioning

confidence: 99%

Highly Selective Asymmetric Rh-Catalyzed Hydroformylation of Heterocyclic Olefins

et al. 2012

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“…However, when monosubstituted spiropentane was subjected to the reaction This all indicates that the carbonylation of spiropentanes forming cyclopentenones also involves two successive carbon-carbon bond cleavage processes which were discussed in the former research [66]. In 2007, based on previous studies on hydroformylation [67][68][69][70][71][72][73][74], it seemed that the application of supramolecular catalysts could solve the problems with low regio-, diastereo-, and enantioselectivity [75][76][77]. Tan and co-workers synthesized a series of scaffolding ligands and tested them in the hydroformylation of terminal olefin (Scheme 39) [78].…”

Section: %mentioning

confidence: 98%

Rhodium-Catalyzed Carbonylative Synthesis of Heterocycles

Feng¹,

Wu²

2015

Topics in Heterocyclic Chemistry

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“…While progress has been made in selective C–H oxidation via transition-metal catalyzed ketone hydroacylation, [1–4] the field is still young compared to that of the related ketone hydrosilylation, [5] olefin hydrogenation, [6] hydroformylation, [7] and hydroacylation [8] transformations. A complication that is common to both olefin and ketone hydroacylation arises from an energetically competent decarbonylation pathway that leads to deactivation of the transition metal catalyst, which has severely limited the efficacy and practicality of these methodologies in the past.…”

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confidence: 99%

Rhodium(I)‐Catalyzed Intermolecular Hydroacylation of α‐Keto Amides and Isatins with Non‐Chelating Aldehydes

2015

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The application of the bidentate, electron-rich bisphosphine ligand, 1,3-bis(dicyclohexyl)phosphine-propane (dcpp), in rhodium(I)-catalyzed intermolecular ketone hydroacylation is herein described. Isatins and α-keto amides are shown to undergo hydroacylation with a variety of non-chelating linear and branched aliphatic aldehydes. Also reported is the synthesis of new bidentate chiral phosphine ligands, and their application in hydroacylation is discussed.

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Asymmetric Hydroformylation

Cited by 50 publications

References 78 publications

Highly Selective Asymmetric Rh-Catalyzed Hydroformylation of Heterocyclic Olefins

Highly Selective Asymmetric Rh-Catalyzed Hydroformylation of Heterocyclic Olefins

Rhodium-Catalyzed Carbonylative Synthesis of Heterocycles

Rhodium(I)‐Catalyzed Intermolecular Hydroacylation of α‐Keto Amides and Isatins with Non‐Chelating Aldehydes

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