Double Asymmetric Induction in the Synthesis of Enantiomeric α‐Aminophosphonic Acids Mediated by Sulfinimines

Abstract

A double asymmetric induction inthe synthesis of α-aminophosphonic acids is described.

Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

“…Finally, the same authors also used 2,3-D-isopropylidene-(R)-glyceraldehyde (90) as chiral aldehyde in the reaction with (−)-56. After extensive experimentation, it was established that the best diastereoselectivity (de 85%) could be obtained with the use of (S)-aluminium lithium bis(binaphthoxide) as a catalyst in THF at room temperature.…”

“…As an example of double asymmetric addition, the use of optically pure (−)- and (+)-lithium salts of O , O -di-(1 R ,2 S ,5 R )-menthyl H -phosphonate ( 76 ) by the hydrophosphonylation of pure enantiomers of both chiral N -( p -tolylsulfinyl)-benzaldimines (+)- and (−)- 77a,b at −78 °C, leading to the corresponding α-aminophosphonates 78 with high diastereoselectivity (dr up to 100 : 0) was reported by Łyżwa (Scheme 25). 90 The enantiomers of (−)- 76a and (+)-( S )- 77a as well as of (+)- 76b and (−)-( R )- 77b were assigned as the matched pairs of isomers, whereas the enantiomers (−)- 76a and (−)-( R )- 77b or (+)- 76b and (+)-( S )- 77a were assigned as the mismatch pairs. In each case, the pure major diastereoisomer was isolated by means of chromatography.…”

The Last Decade of Optically Active α-Aminophosphonates

“…The enantiomeric purities were between 72 and 96% (Scheme 18) [30]. A thiourea-coupled cinchona alkaloid-catalyzed (51) aza-Henry reaction of iminophosphonates (52) and nitromethane provided the corresponding α-aminophosphonates (53) under mild conditions in good yields, and with enantiomeric excesses (Scheme 19) [31]. This addition method has the advantage of 100% atomic efficiency.…”

“…The addition of the two optically active dimenthyl phosphites (101, R 2 = menthyl) to N-(p-tolylsulfinyl)-benzaldimine (107) afforded the corresponding sulfonyl-aminophosphonates (108) in a diastereomeric ratio of 91/100%. A subsequent acidic hydrolysis of the two sulfonyl-aminophosphonates (108) gave the corresponding optically active, free αaminophosphonic acids (109) in 72/75% (Scheme 37) [52,53]. α-Amido sulfones were suitable starting materials in the preparation of C-chiral α-aminophosphonic derivatives, using the above mentioned chiral phosphite (105) [51].…”

“…The addition of the two optically active dimenthyl phosphites (101, R 2 = menthyl) to N-(p-tolylsulfinyl)-benzaldimine (107) afforded the corresponding sulfonyl-aminophosphonates (108) in a diastereomeric ratio of 91/100%. A subsequent acidic hydrolysis of the two sulfonylaminophosphonates (108) gave the corresponding optically active, free α-aminophosphonic acids (109) in 72/75% (Scheme 37) [52,53]. 1,2-cyclohexylenediamine-related bis(phenylmethylphosphonates) (111) were synthetized from the corresponding optically active bis-imine (110) and dialkyl phosphites in a diastereoselective manner without the use of any catalyst.…”