Desymmetrizing Hydroformylation of Diallylcarbinols with the Aid of a Planar‐Chiral, Catalyst‐Directing Group

Abstract

The desymmetrizing hydroformylation of diallylcarbinols has been achieved by employing a planar-chiral, substratebound catalyst-directing group − the ortho-(diphenylphosphanyl)ferrocenylcarbonyl group (o-DPPF). The method allows the simultaneous construction of two stereogenic centers in a 1,3-relative position with high levels of stereocontrol. The diastereoselectivity was investigated as a function of substrate structure. Determination of the relative and absolute configuration of the product aldehydes (chemical

Transition metals in organic synthesis: Highlights for the year 2005

“…(196)) [39]. (195) (196) Rhodium catalyzed a desymmetrizing hydroformylation of diallylcarbinols [981]. A rhodium-catalyzed hydroformylation-Fischer indole synthesis sequence was described (Eq.…”

Removable Directing Groups in Organic Synthesis and Catalysis

“…The corresponding anti-aldehydes 51 were obtained in good yields, excellent diastereoselectivities, and in enantiomerically pure form (Table 11). [52] Similar to the previous case, a rationale for the stereochemical course of the o-DPPF-directed hydroformylation of diallylcarbinols was proposed by comparison of the four diastereomeric chelating rhodium-alkene complexes E-H (Scheme 44). Thus complexes E and F compete for facial diastereoselection, while comparison of the stabilities of complexes G and H versus E and F can explain the discrimination of the diastereotopic groups.…”

Chiral Ligands for Rhodium‐Catalyzed Asymmetric Hydroformylation: A Personal Account

“…Although good regio‐ and enantioselectivities have been achieved for the AHF reaction of many substrates, such as monosubstituted and ( Z )−1,2‐disubstituted olefins, only very limited examples are involved in Rh‐catalyzed desymmetrizing AHF 37–41. Employing the desymmetrizing AHF strategy to the catalytic synthesis of chiral aldehydes with high diastereoselectivities and enantioselectivities is still a challenge.…”