Recent advances in the diastereoselective Reformatsky-type reaction

Abstract

The classical Reformatsky reaction introduced for the first time in 1887 has been recognized as one among the most useful methods for C-C bond formation. Diastereoselective versions based on the use of chiral auxiliaries as well as enantioselective protocols using chiral ligands have been successfully developed during the last few years. This tutorial review highlights the main recent achievements (since 2004) in the diastereoselective Reformatsky reaction; diastereochemical control has been efficiently achieved using a large variety of chiral auxiliaries to perform the synthesis of specific cyclic and acyclic chiral moieties. The diastereoselective Reformatsky reactions employed in the total synthesis of natural products are also described.

Applications of ultrasound in total synthesis of bioactive natural products: A promising green tool

“…This reaction is very useful to create a new C–C bond and it includes good functional group tolerance. For this reason, this reaction has been employed in the preparation of biologically active products [28] , [29] , [30] ; the use of nitriles as electrophiles to produce potentially useful β-ketoesters in the field of medicinal chemistry [31] , [32] . Yue et al accomplished a total synthesis of natural ( S )-(+)-dihydrokavain ( 9 ) from the chiral aldehyde ( 6 ) via a green methodology that includes a sonochemical Blaise reaction as the key step [33] .…”

Recent developments in the asymmetric Reformatsky-type reaction

“…Furthermore, the challenging field of catalytic enantioselective (aza)-versions is fast-growing since the discovery that ZnMe 2 or ZnEt 2 could be used as zinc sources allowing more convenient homogeneous reaction conditions to be used [ 2 – 3 ]. This review collects the important developments in asymmetric Reformatsky-type reactions published since the beginning of 2013, since this field was most recently reviewed this year by Colobert for the diastereoselective version [ 4 ], and Fernández-Ibáñez and Maciá for the catalytic enantioselective version [ 5 ]. Earlier, this field was reviewed by different groups [ 6 – 13 ].…”

Selective Synthesis of Trifluoromethyl β‐Lactams by a Zn‐Promoted 2‐Bromo Ester Addition on C‐CF3‐Substituted Aldimines

“…Unfortunately, imino‐Reformatsky reactions are problematic and often lead to mixtures of β‐amino esters and corresponding β‐lactams. As a major consequence, the enantio‐ and/or diastereoselective studies are slightly explored despite their synthetic and applications potential. Even more interesting is obtaining fluorinated precursors because of the known effects of fluorine atom inclusion on bioactive molecules .…”