Asymmetric hydroformylation of 1,2-disubstituted olefins catalysed by chiral phosphinephosphite–rhodium(<scp>I</scp>) complexes

Sakai, Nozomu; Nozaki, Kyoko; Takaya, Hidemasa

doi:10.1039/c39940000395

Cited by 131 publications

(34 citation statements)

References 6 publications

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“…BINAPHOS) have been employed in asymmetric hydroformylation reactions [19] with no isomerization activity and very low reaction rates for internal olefins. [20] Indeed, as can be seen from Table 3, 1-butene reacts with much higher rates (factor 40, entry 1) than the internal olefin (entry 3). If a larger excess of ligand is used, no significant increase of regioselectivity is observed; this confirms the chelating binding mode of the ligand to the transition metal center (entries 1 and 2).…”

Section: Resultsmentioning

confidence: 92%

Dual Catalytic Systems for Consecutive Isomerization-Hydroformylation Reactions

Beller¹,

Zimmermann²,

Geissler³

1999

Chem. Eur. J.

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A concept for the homogeneous hydroformylation of internal olefins to linear aldehydes is presented. The internal olefin is isomerized to its terminal isomer by one catalyst prior to hydroformylation by a second transition metal catalyst. The terminal olefins obtained by isomerization react preferentially to give linear aldehydes. The viability of the concept is demonstrated by a dual catalytic Ru/Rh system with chelating phosphanophosphite ligands. Thus, the isomerization ± hydroformylation sequence represents a promising starting point for the economically important refinement of internal olefins.

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Section: Resultsmentioning

confidence: 92%

Dual Catalytic Systems for Consecutive Isomerization-Hydroformylation Reactions

Beller¹,

Zimmermann²,

Geissler³

1999

Chem. Eur. J.

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“…In the Rh-catalyzed asymmetric hydroformylation of 1,2-alkyl-disubstituted alkenes (Scheme 16) as substrates, the BINAPHOS ligand 40 provided the highest ee values [92,93]. Interestingly, it was reported that the E-isomers 4d and 4f yielded lower enantioselectivity than their Z-counterparts 4c and 4e.…”

Section: Linear 12-disubstituted Alkenesmentioning

confidence: 96%

“…The 1,3-diphosphite ligand 26 was used in the Rh-catalyzed asymmetric hydroformylation of trans-anethole 4a and estragole 4b (Scheme 15) but moderate to low enantioselectivities were achieved (ee up to 15%) [91]. Nozaki et al reported the asymmetric Rh-catalyzed hydroformylation of transanethole 4a into 5a using the BINAPHOS ligand 40 with excellent regioselectivity (98%) and a remarkable 80% ee [92,93].…”

Section: Linear 12-disubstituted Alkenesmentioning

confidence: 97%

“…It is therefore required to limit the isomerization in order to obtain high selectivities. In the Rh-catalyzed asymmetric hydroformylation of 2,5-dihydrofuran 4k, Nozaki et al reported the first successful results using the BINAPHOS ligand 40 which yielded total regioselectivity to the tetrahydro-3-carbaldehyde 5k with 68% ee (R) (Scheme 21) [92,93,100]. However, when the 2,3-dihydrofuran 4n was tested with the same catalyst, no regioselectivity was observed and the ee obtained for the (40) and (57) aldehyde 5k decreased to 38% with S configuration.…”

Section: Monocyclic 12-disubstituted Alkenesmentioning

confidence: 97%

“…The asymmetric Rh-catalyzed hydroformylation of dioxapines 4q, r was reported using the BINAPHOS ligand 40 and 1,3-diphosphite ligands derived from carbohydrates 61b (Scheme 21) [92][93][94][95][96][97][98][99][100]102]. Using the ligand 40, total regioselectivity to 5q, r was achieved, together with ees up to 76%.…”

Section: Monocyclic 12-disubstituted Alkenesmentioning

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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Controlling Stereoselectivity with the Aid of a Reagent-Directing Group: Hydroformylation, Cuprate Addition, and Domino Reaction Sequences

Breit¹

2000

Chem. Eur. J.

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Asymmetric hydroformylation of 1,2-disubstituted olefins catalysed by chiral phosphinephosphite–rhodium(I) complexes

Cited by 131 publications

References 6 publications

Dual Catalytic Systems for Consecutive Isomerization-Hydroformylation Reactions

Dual Catalytic Systems for Consecutive Isomerization-Hydroformylation Reactions

Asymmetric Hydroformylation

Controlling Stereoselectivity with the Aid of a Reagent-Directing Group: Hydroformylation, Cuprate Addition, and Domino Reaction Sequences

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