A Protocol for Direct Stereospecific Amination of Primary, Secondary, and Tertiary Alkylboronic Esters

Abstract

The direct, stereospecific amination of alkylboronic and borinic esters can be conducted by treatment of the organoboron compound with methoxyamine and potassium tert-butoxide. In addition to being stereospecific, this process also enables the direct amination of tertiary boronic esters in an efficient fashion.

Enantioselective Construction of Tertiary Boronic Esters by Conjunctive Cross‐Coupling

“…15 Conjunctive coupling followed by a modified Tamao-Fleming oxidation 16 furnished 37 , a known precursor 17 to 38 . Also as depicted in Figure 1, the analgesic agent 41 was easily assembled by conjunctive coupling followed by amination 18 and conversion of the intermediate amine group to an isocyanate ( 40 ); intramolecular substitution 19 furnished the isoquinolone 41 .…”

Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis

“…In addition, use of sterically demanding 2-MeC 6 H 4 Br did not impede the reaction (product 8). Various heterocycles (products [11][12][13][15][16][17] as well as an alkenyl bromide were also tolerated (product 14). In addition, alkene 19 could be used and allowed for control of stereochemistry with respect to the existing stereogenic center.…”

Automated stereocontrolled assembly-line synthesis of organic molecules

“…In order for fully automated syntheses of organic molecules to be achieved, it is important that a single robotic platform has the capability to perform diverse chemical reactions. Therefore, we subsequently investigated the conversion of boronic ester 10 into amide 11, which requires the transformation of the boronic ester moiety into a primary amine, [25][26] followed by acylation and methylation (Fig. 3C).…”