Branched‐Regioselective Hydroformylation with Catalytic Amounts of a Reversibly Bound Directing Group

Grünanger, Christian U.; Breit, Bernhard

doi:10.1002/anie.200802296

Cited by 127 publications

(55 citation statements)

References 29 publications

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“…When (À)-myrtenol was treated in analogous reaction conditions, the stereoselective formation of the cyclic hemiacetal 117 was observed ( Scheme 24 [b]). Terminal and internal bishomoallylic alcohols can HF with high regio-and diastereoselectivity, employing a catalytic amount of a catalyst-directing group, enabling atom-economical preparation of a wide range of γ-lactols and lactones (Scheme 25) [63].…”

Section: Tandem Hf In the Presence Of O-nucleophilesmentioning

confidence: 99%

Domino Reactions Triggered by Hydroformylation

Petricci

Cini

2013

Topics in Current Chemistry

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Section: Tandem Hf In the Presence Of O-nucleophilesmentioning

confidence: 99%

Domino Reactions Triggered by Hydroformylation

Petricci

Cini

2013

Topics in Current Chemistry

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“…The term "catalyst-directing groups" was defined for organocatalysts that are able to form simultaneously covalent bonds with a substrate and dative bonds with a metal catalyst, which allow them to direct metal-catalyzed transformations [118]. In general, these "scaffolding ligands" were named by analogy with scaffolding proteins, which promote biological processes [119].…”

Section: Scaffolding Ligandsmentioning

confidence: 99%

“…In general, these "scaffolding ligands" were named by analogy with scaffolding proteins, which promote biological processes [119]. Using such methodology, the groups of Tan and Breit reported the highly regioselective Rh-catalyzed hydroformylation of homoallylic alcohols [118,120]. Tan et al designed the alkoxy benzoazaphosphole ligand 67 derived from N-methyl aniline that undergoes facile exchange with other alcohols or secondary amines (Scheme 29) [120].…”

Section: Scaffolding Ligandsmentioning

confidence: 99%

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Asymmetric Hydroformylation

Perandones

Godard

Claver

2013

Topics in Current Chemistry

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Rhodium is currently the metal of choice to achieve high enantioselectivities in the hydroformylation of a relatively wide variety of alkene substrates. The elucidation of the different steps of the catalytic cycle and the characterization of the resting state, together with the discovery of several types of ligands that are able to provide high enantioselectivities, have made the rhodium-catalyzed hydroformylation a synthetically useful tool. For years, ligands containing phosphite moieties such as diphosphites and phosphine-phosphites were considered the most successful ligands to achieve high enantioselectivities for classical substrates such as styrene and vinyl acetate. In fact, the phosphite-phosphine BINAPHOS (43) and its derivatives are still today the most successful ligands in terms of selectivity and scope. For more substituted substrates, general trends can be extracted. However, recent studies showed that these general trends can be sometimes reversed by the use of the appropriate catalyst and choice of reaction conditions, clearly showing that these trends are only indicative and that there are still many challenges to be tackled in this area.

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“…[1] It can be carried out in numerous ways, for example, Lewis acid or base activation, hydrogen bond activation, enamine formation, iminium formation, metal complexation, etc. [2][3][4][5] However, most catalytic reactions through above ways usually operate by performing the activation of one or both substrates.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study on the mechanism of the reaction for alkene hydroaminations catalyzed by chiral aldehyde

Zhao

Sun

et al. 2013

Int J of Quantum Chemistry

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Alkene hydroamination catalyzed by chiral aldehyde relying only on temporary intramolecularity is a new concept reaction. In this article, the reaction mechanism was investigated using density functional theory. The calculation results show that: (1) The reaction can be divided into two parts. The first part is a dehydration process involving a hemiaminal formation. The nitrone catalyst forms through rapid intermolecular nucleophilic addition of benzylhydroxylamine to chiral aldehyde precatalyst. The second part is a catalytic cycle, which involves an aminal formation-hydroamination-ring opening-product release process. (2) There are four enantioselective pathways related to the products of S and R configurations. Enantioselectivity is attributed to the different forming ways of a planar five-membered ring. The preferred pathways for the S-configuration product (S3) and R-configuration product (R3) are confirmed.

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Branched‐Regioselective Hydroformylation with Catalytic Amounts of a Reversibly Bound Directing Group

Abstract: Phosphinites do the trick and work as reversibly bound catalyst‐directing groups in catalytic amounts to allow for the highly regioselective hydroformylation of homoallylic alcohols with terminal and internal alkene functions in favor of the branched product.

Cited by 127 publications

References 29 publications

Domino Reactions Triggered by Hydroformylation

Domino Reactions Triggered by Hydroformylation

Asymmetric Hydroformylation

Theoretical study on the mechanism of the reaction for alkene hydroaminations catalyzed by chiral aldehyde

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