Rhodium‐Catalyzed Asymmetric Hydroformylation of N‐Allylamides: Highly Enantioselective Approach to β²‐Amino Aldehydes

Abstract

N‐Allylamide und N‐Allylsulfonamide wurden mithilfe eines Rhodium‐Yanphos‐Katalysators asymmetrisch hydroformyliert. Dabei wurden β2‐Aminoaldehyde, ‐säuren und ‐alkohole mit ausgezeichneten Enantioselektivitäten erhalten (siehe Schema; TON=Umsatzzahl, acac=Acetylacetonat).

A concise access to bridged [2,2,1] bicyclic lactones with a quaternary stereocenter via stereospecific hydroformylation

“…Asymmetric hydroformylation (AHF) represents an efficient approach for asymmetric formation of C–C bond in an atomic economic manner 17 – 25 , and the aldehyde products can be easily converted to versatile functional compounds, such as chiral alcohols, acids, amines and esters 26 – 34 , thus AHF has been widely investigated and some significant progresses have been made 35 – 45 . However, most of the work focused on the AHF of monosubstituted olefins and disubstituted alkenes, and only one chiral center was introduced into the product.…”

Stereospecific Hydroformylation of 1-Substituted Cyclopent-3-en-1-ols: A Concise Access to Bridged [2, 2, 1] Bicyclic Lactones With A Quaternary Stereocenter

“…16 Therefore, the development of a concise and efficient method to produce bridged [2,2,1] bicyclic lactones is highly desirable. Asymmetric hydroformylation (AHF) represents an efficient approach for asymmetric formation of C-C bond in an atomic economic manner, 17,18,19,20,21,22,23,24,25 and the aldehyde products can be easily converted to versatile functional compounds, such as chiral alcohols, acids, amines and esters, 26,27,28,29,30,31,32,33,34 thus asymmetric hydroformylation has been widely investigated and some significant progress have been made. 35,36,37,38,39,40,41,42,43,44,45 However, asymmetric hydroformylation is very sensitive to the steric hindrance of substrate, which make it difficult to tolerate tri-or tetrasubstituted alkenes.…”