Atropisomeric diastereoisomers from nucleophilic attack on 8-acyl-1-naphthamides

First Use of Axially Chiral Thioamides for the Stereocontrol of C−C Bond Formation

“…Introduction of steric hindrance has led to acceptable or significant barriers to rotation along the axis of chirality and opened the way to ™atroposelectivity∫. Reactions that have been stereocontrolled in this fashion include the alkylation and aldol reactions of enolates, [10,11,14,15] nucleophilic addition to carbonyl derivatives [16,17] and iminium salts, [18] addition of electrophiles to ortho or laterally metalated naphthamides, [3, 19±21] Diels ± Alder and dipolar cycloadditions, [12,22] and radical reactions. [6,23] We wished to replace the oxygen atom of amides by a sulfur atom, as there seems to be no precedent for the use of atropisomeric thioamides in asymmetric synthesis, and believe that this will present a number of useful characteristics.…”

Atropisomeric benzamides and naphthamides as chiral auxiliaries †

“…In a series of publications, [1][2][3][4][5][6][7][8][9][10][11] we have demonstrated that the stereogenic axis of hindered, atropisomeric tertiary aromatic amides of general structure 1 is capable of controlling high levels of stereoselectivity. We have also described two ways of making this class of atropisomeric compounds as single enantiomers, 12, 13 both involving the control of axial stereochemistry by the conformational influence of an adjacent stereogenic centre.…”

Atroposelective attack of nucleophiles and electrophiles on 2-acyl-1-naphthamides and their enolates

“…This paper will discuss nucleophilic attack on 2-acyl-1-naphthamides 44 and electrophilic attack on their enolates. 45 The next paper 46 will discuss 2-formyl-1-naphthamides and their derivatives, and will highlight the role of metal-carbonyl coordination in their reactions, and the third paper 47 will discuss the stereoselective reactions of 8-acyl-1naphthamides.…”