A Unified Strategy for the Asymmetric Synthesis of Highly Substituted 1,2-Amino Alcohols Leading to Highly Substituted Bisoxazoline Ligands

Abstract

A general procedure for the asymmetric synthesis of highly substituted 1,2-amino alcohols in high yield and diastereoselectivity is described that uses organometallic additions of a wide range of nucleophiles to tertbutylsulfinimines as the key step. The addition of organolithium reagents to these imines follows a modified Davis model. The diastereoselectivity for this reaction depends significantly on both the nucleophile and electrophile. These highly substituted 1,2-amino alcohols are used to synthesize stereochemically diverse and structurally novel, polysubstituted 2,2′-methylene(bisoxazoline) ligands in high yields.

Kukhtin–Ramirez-Reaction-Inspired Deprotection of Sulfamidates for the Synthesis of Amino Sugars

“…Amino alcohols are important skeletons which are widely distributed in pharmaceuticals and biologically active natural products (Figure 1a) [1][2][3]. Amino alcohols also play important roles in organic synthesis as synthons, ligands, auxiliaries, and chiral catalysts [4][5][6][7][8]. This significance has inspired tremendous efforts to devise elegant synthetic methods for the construction of amino alcohols [9][10][11][12][13][14][15].…”

Catalytic, Enantioselective Syn-Oxyamination of Alkenes

“…Given the importance of enantioenriched 1,2-amino alcohols, versatile and modular strategies to access these motifs are of great synthetic interest. Accordingly, a number of approaches have been developed for the assembly of enantioenriched 1,2-amino alcohols from a diverse array of starting materials, such as alcohols, aldehydes, ketones, amino acids, and amino esters . Although these multistep syntheses provide good yields and enantioselectivities, a one-step protocol would offer the distinct advantage of a more efficient construction for more rapid generation of molecular complexity.…”

“…Accordingly, a number of approaches have been developed for the assembly of enantioenriched 1,2-amino alcohols from a diverse array of starting materials, such as alcohols, aldehydes, ketones, amino acids, and amino esters. 5 Although these multistep syntheses provide good yields and enantioselectivities, a one-step protocol would offer the distinct advantage of a more efficient construction for more rapid generation of molecular complexity. Alkene difunctionalization, and more specifically alkene 1,2-oxyamination, offers a potentially modular approach to the assembly of 1,2-amino alcohols and has garnered considerable recent interest.…”

Cobalt-Catalyzed Asymmetric Hydrosilylation of α-Oxygenated Ketones

“…Optically pure 1,2-diols represent an important class of synthons in organic chemistry and have a wide range of applications for the preparation of biologically and pharmaceutically active compounds, chiral auxiliaries, and ligands . Thus, great attention has been paid to the preparation of chiral 1,2-diols.…”