2019
DOI: 10.1002/anie.201811888
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High iso Aldehyde Selectivity in the Hydroformylation of Short‐Chain Alkenes

Abstract: The hydroformylation of propene to give predominantly iso-butanal has been achieved; class-leading selectivity is possible even at higher temperatures that deliver fast rates. Racemic Rh complexes of bidentate phospholane phosphites derived from tropos-biphenols and unusual solvent systems are the key to the selectivity observed.

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Cited by 45 publications
(43 citation statements)
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“…Rh catalysts with bidentate ligands dominate the scene, especially with substrates with directing groups 22 . At present, the branched-selective hydroformylation of olefins without directing groups is still challenging and can be achieved only by complex Rh catalysts with a selectivity for 2-methylhexanale from 1hexene up to 75% 23,24 and up to 86% for 2-methylbutanale from 1-butene 25 . Supramolecular chemistry has also been used to tune regioselectivity in Rh-catalysed hydroformylation [26][27][28] .…”
mentioning
confidence: 99%
“…Rh catalysts with bidentate ligands dominate the scene, especially with substrates with directing groups 22 . At present, the branched-selective hydroformylation of olefins without directing groups is still challenging and can be achieved only by complex Rh catalysts with a selectivity for 2-methylhexanale from 1hexene up to 75% 23,24 and up to 86% for 2-methylbutanale from 1-butene 25 . Supramolecular chemistry has also been used to tune regioselectivity in Rh-catalysed hydroformylation [26][27][28] .…”
mentioning
confidence: 99%
“…The commercial processes occur in the presence of either Rh or Co catalysts whose inherent selectivity favors the formation of n ‐butanal over isobutanal [2–4] . The increasing demand for isobutanal‐derived materials, such as plasticizers, coatings, solvents, cleaners, food additives, or extractants for pharmaceutical products, as well as the unmatched challenge of developing catalysts featuring the isoselectivity, have driven significant research [5–20] . However, limited progress has been achieved thus far and no methods have been commercialized.…”
Section: Figurementioning
confidence: 99%
“…While hydroformylation reactions have been extensively studied and broadly applied in academia and industry for almost a century, many challenges remain unsolved. In particular, noteworthy are (i) regioselectivity issues, including branchedselectivity for terminal alkyl alkenes, [81][82][83][84][85][86][87][88][89][90] β-selectivity for (hetero)aryl alkenes [91][92][93][94] , or any site-selectivity for unsymmetrical internal alkenes and alkynes, [73,[95][96][97][98][99] (ii) chemoselectivity issues, including hydrogenation side-processes in reactions of alkynes or isomerization processes of internal alkyl alkenes, as well as (iii) activity issues in reactions of terminal alkynes, all of which proved to be difficult to address comprehensively with the most common Rh-and Co-catalysis. On the other hand, the catalytic capacity of complexes of other metals was established many years ago, [30,42] but they remained understudied with few reports appearing sporadically.…”
Section: Discussionmentioning
confidence: 99%