Chiral N-phosphonyl imine chemistry: asymmetric 1,2-additions of allylmagnesium bromides

Chiral N-phosphonyl imine chemistry: asymmetric additions of glycine enolate to diphenyl diamine-based phosphonyl imines

“…Among these methods the reaction of chiral imines with glycine enolate has become one of the most powerful and practical tool for this synthesis [23][24][25]. Very recently, we established (1R,2R)-diamino-cyclohexane based phosphonyl imine chemistry [26][27][28][29][30][31][32][33][34] and developed an efficient procedure for the asymmetric synthesis of α-β diamino esters with good to excellent yields and diastereoselectivity [34].…”

“…Later, the replacement of (1R,2R)-1,2-diphenylethylene diamine with (1R,2R)-diaminocyclohexane resolved this problem and the (1R,2R)-diaminocyclohexane based chiral phosphonyl imines with different N-protecting groups were successfully utilized in many nucleopholic addition reactions [26][27][28][29][30][31][32][33][34]. Nevertheless, the 1,2-diphenylethylene diamine based phosphonyl imines are still of great value since they can extend structure scope of this important phosphonyl imines.…”

Asymmetric C–C Bond Formation between Chiral N‐Phosphonyl Imines and a Nickel(II)‐Complexed Glycine Schiff Base Provides Efficient Synthesis of α,β‐syn‐Diamino Acid Derivatives

“…6–7 Ideally, the auxiliaries should also be cleavable under convenient conditions and recycled for re-use. 4 …”

“…In the past several years, the N -phosphonyl and N -phosphinyl functional group-based GAP chemistry has been proven to meet the above purposes; 4–7 this is attributed to the unique polarity of P=O bonds in which negative and positive charges are heavily localized on oxygen and phosphorous atoms.…”

Stereoselective Addition of Grignard Reagents to New P‐Chirogenic N‐Phosphinoylbenzaldimines: Effect of the Phosphorus Substituents on the Stereoselectivity

“…Although (diphenylphosphinoyl)imines are by far the most common electrophiles used in the stereoselective addition of nucleophiles with chiral metal-complex catalysts, [4] rare examples of chiral phosphinoylimines bearing a P-chirogenic center or a chiral auxiliary linked to the P atom can be found in the literature. Very recently, Li and co-workers reported the synthesis of chiral C 2 -symmetric phosphinoylimines derived from secondary enantiopure trans-cyclohexane-1,2-diamine, which were successfully used as electrophiles in asymmetric reactions such as azaDarzens, [5] aza-Henry, [6] and Mannich reactions, [7] the addition of Grignard reagents [8] and various enolates, [9] and very recently in the addition of lithium aryl-and alkylacetylides [10] and lithium phosphites [11] with excellent results in terms of yields and diastereomeric excesses of the final products. In 1994, Jennings et al reported the synthesis of N-[(mesityl)(phenyl)phosphinoyl]benzaldimine and the oxidation of the C=N double bond leading to new chiral oxaziridines, [12] important reagents in the asymmetric oxidation of prochiral sulfides and olefins.…”