Advances in the hydroformylation of olefins containing functional groups

Botteghi, C.; Ganzerla, Renzo; Lenarda, Maurizio; Moretti, Giuseppe

doi:10.1016/0304-5102(87)80033-0

Cited by 120 publications

(31 citation statements)

References 53 publications

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“…For reaction of methyl atropate at 100 8C, (Scheme 3; Table 2; entries [11][12][13][14], the amount of linear product reduces dramatically with an increase in pressure and the amount of hydrogenation is also reduced. In experiments in which the pressure was kept constant (entries 14-18), the amount of linear product and hydrogenation decreased with decreasing temperature.…”

Section: Resultsmentioning

confidence: 99%

“…[5][6][7][8][9][10][11][12][13] However, despite these precedents, hydroformylation is underused in organic syntheses, with little known about how more complex substrates perform in this reaction. [14][15][16] Low-molecular-weight, densely functionalised aldehydes are very important building blocks, in particular for the synthesis of secondary amines. Secondary amines are an extremely common motif in compounds of pharmaceutical interest, with reductive amination the workhorse for their preparation.…”

Section: Introductionmentioning

confidence: 99%

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Highly Regioselective Rhodium‐Catalysed Hydroformylation of Unsaturated Esters: The First Practical Method for Quaternary Selective Carbonylation

Clarke

Roff

2006

Chemistry A European J

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Highly regioselective hydroformylation of unsaturated esters can be achieved when a highly reactive, ligand-modified, rhodium catalyst is employed near ambient temperatures (15-50 degrees C) and pressures over 30 bar. The use of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane shows distinct advantages over other commonly applied phosphanes in terms of reaction rate, and regio- and chemoselectivity. Hydroformylation of a range 1,1-di- and 1,1,2-trisubstituted unsaturated esters yields quaternary aldehydes that are forbidden products according to Keulemans Rule. The aldehydes can be reductively aminated with molecular hydrogen to give beta-amino acid esters in high yield. The overall green chemical process involves converting terminal alkynes into unusual beta-amino acid esters with only water generated as an essential byproduct. This catalytic system has also been applied to the hydroformylation of simple 1,2-disubstitued unsaturated esters, which have been hydroformylated with excellent alpha-selectivity and good chemoselectivity for the first time.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly Regioselective Rhodium‐Catalysed Hydroformylation of Unsaturated Esters: The First Practical Method for Quaternary Selective Carbonylation

Clarke

Roff

2006

Chemistry A European J

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“…[5] In general, phosphanerhodium catalysts display much higher activities for terminal olefins than for internal olefins, which are converted very slowly with little isomerization. [6] Coordinatively unsaturated rhodium species, however, exhibit activity towards isomerization of the substrate. Such unsaturated species are formed in the presence of sterically demanding phosphites or phosphanes.…”

Section: Scheme 1 Hydroformylation Of Terminal Olefinsmentioning

confidence: 99%

Synthesis of Pyrrolyl-, Indolyl-, and Carbazolylphosphanes and Their Catalytic Application as Ligands in the Hydroformylation of 2-Pentene

et al. 2001

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The synthesis of π-acceptor ligands of the type PAr x R 3−x (x = 0−2; R = pyrrolyl, indolyl, carbazolyl; Ar = aryl) (1−8, 10, 12, 13) and P(pyrrolyl) 2 (carbazolyl) (11) is described. These ligands can be prepared in good to excellent yields by treatment of the corresponding free heterocyclic amines with phosphorus chlorides in the presence of base. The utilization of pyrrolyl-, indolyl-, and carbazolylphosphanes in the rhod-

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“…In contrast to cobalt catalysts, rhodium phosphane systems show a much higher activity for terminal olefins, and internal olefins are converted only very slowly to branched aldehydes with little isomerization. [9] Like cobalt catalysts, coordinatively unsaturated rhodium species exhibit activity towards isomerization of the olefinic substrate.…”

Section: Introductionmentioning

confidence: 99%

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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Advances in the hydroformylation of olefins containing functional groups

Cited by 120 publications

References 53 publications

Highly Regioselective Rhodium‐Catalysed Hydroformylation of Unsaturated Esters: The First Practical Method for Quaternary Selective Carbonylation

Highly Regioselective Rhodium‐Catalysed Hydroformylation of Unsaturated Esters: The First Practical Method for Quaternary Selective Carbonylation

Synthesis of Pyrrolyl-, Indolyl-, and Carbazolylphosphanes and Their Catalytic Application as Ligands in the Hydroformylation of 2-Pentene

Dual Catalytic Systems for Consecutive Isomerization-Hydroformylation Reactions

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