Diphosphines with natural bite angles near 120.degree. increase selectivity for n-aldehyde formation in rhodium-catalyzed hydroformylation

Casey, Charles P.; Whiteker, Gregory T.; Melville, Margaret G.; Petrovich, Lori M.; Gavney, James A.; Powell, Douglas R.

doi:10.1021/ja00040a008

Cited by 401 publications

(250 citation statements)

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“…For instance, when the bite angle of diphosphane increases from 788 (dppe, 1) to 1078 (trans-dppm-cyp, 2) to 1128 (bisbi, 3), the n:iso ratio increases from 1 to 5-8 to 25 (Table 1). [18] However, 2,5-dppmnor (4), which has a wide natural-bite angle (1268) gave only lower n:iso ratio (2.6) because of its inability to form stable chelates.…”

Section: Hydroformylationmentioning

confidence: 99%

“…When E ¼ 6 H, a more general statement nowadays is "When adding (a polar compound) to the double bond of unsymmetrical alkenes, the initial electrophile prefers to add to the primary (18) carbon the most, the secondary (28) carbon next, and the tertiary (38) carbon least." [5] Thus, in the case of hydroboration, hydrosilylation, hydrostannation, etc., in which H is the nucleophile, a formal anti-Markovnikov product is formed.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

et al. 2004

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The regioselective functionalization of terminal alkenes and alkynes is of utmost importance for the synthesis of a wide variety of organic products. Based on the original observation by Vladimir Markovnikov-the pioneer of this field of research-in the 19th century, the possible regioisomeric products are classified as Markovnikov or anti-Markovnikov products. Contrary to traditional belief, it is nowadays possible to control the regiochemistry of various additions of nucleophiles to alkenes and alkynes by applying different transition-metal catalysts. Recent developments in this area of selective functionalization of alkenes and alkynes are reviewed.

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Section: Hydroformylationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

et al. 2004

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“…Casey and co-workers were the ®rst to report that the bite angle of bidentate diphosphines can have a dramatic in¯uence on the regioselectivity of the rhodium catalysed hydroformylation of 1-alkenes [12,13]. They studied in detail a ligand developed by workers at Eastman, 2,2 H -bis((diphenylphosphino)methyl)- and found that the bite angle of this ligand is <1208 and that the preferential mode of co-ordination is bisequatorial.…”

Section: Hydroformylationmentioning

confidence: 99%

The bite angle makes the catalyst

Leeuwen¹,

Kamer²,

Reek³

1999

Pure and Applied Chemistry

105

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Catalytic reactions are described for metal complexes containing bidentate phosphine ligands that enforce wide bite angles in the complexes. The calculated natural bite angles are in the range 100±1208. Three applications will be discussed: (i) nickel catalysed hydrocyanation, for which the ®rst active phosphine catalyst was found, (ii) palladium catalysed allylic alkylation, for which the selectivity also strongly depends on the bite angle, and (iii) rhodium catalysed hydroformylation, which leads to highly linear products.

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“…Casey and co-workers defined the 'natural bite angle' as the preferred chelation angle, which was determined only by ligand backbone constraints, but did not take metal valence angles into consideration. [11] Therefore, the good results made by Xantphos derivatives (I) and calixarene-based diphosphites (II) might be related to the rigid backbone. Tolman found that pyrrolyl substituents on the phosphorus atom could form highly Lewis acidic phosphorus ligands.…”

Section: Introductionmentioning

confidence: 99%

Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives

Zheng

Mo²,

Liang

et al. 2013

Applied Organom Chemis

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Different kinds of mono-and bidentate phosphite ligands were used in Rh-catalyzed hydroformylation of styrene to illustrate the influence of steric and electronic properties of ligands on catalytic performance. High activity (99.9%) and good regioselectivity (85.4%) to the linear aldehyde were achieved under optimum conditions in the presence of Rh/bisphosphite complex (bisphosphite: 2,2 0 -bis(dipyrrolylphosphinooxy)-1,1 0 -(AE)-binaphthyl). This system makes it possible to prepare functionalized terminal aldehydes from readily available styrene or its derivatives through hydroformylation with high linear selectivity.

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Diphosphines with natural bite angles near 120.degree. increase selectivity for n-aldehyde formation in rhodium-catalyzed hydroformylation

Cited by 401 publications

References 0 publications

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and Trends

The bite angle makes the catalyst

Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives

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