Controlling stereochemistry during oxidative coupling. Preparation of Rp or Sp phosphoramidates from one P-chiral precursor

Chemical Communications

Volumn , Issue 22, 2004, Pages 2566-2567

  Nilsson, Johan ^a   Stawinski, Jacek ^a,b  

^a STOCKHOLM UNIVERSITY   (Sweden)

^b POLISH ACADEMY OF SCIENCES   (Poland)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; ESTER DERIVATIVE; IODINE; PHOSPHONIC ACID DERIVATIVE; PHOSPHORAMIDIC ACID DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BOND; CHEMICAL STRUCTURE; CHIRALITY; OXIDATION KINETICS; PRECURSOR; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

EID: 9944227718     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b411451e     Document Type: Article

References (22)

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20. P = -43.14 ppm). These, upon addition of n-butylamine or aniline afforded the same diastereomers of 4a and 4b as those observed when the oxidative couplings were carried out in the presence of these amines; During oxidation of H-phosphonate 1 into phosphoroiodidate 2 (Scheme 1), a substituent of the lowest priority according to the CIP rules (the hydrogen atom bound to phosphorus) is replaced by a substituent of the highest priority (iodine), and thus the notation changes from 1 Rp to 2 Sp (and vice versa), although the reactions occur with retention of configurations. On the other hand, in the reaction of phosphoroiodidate 2 or phosphorochloridate 3 with amines, a substituent of the highest priority (iodine or chlorine atom) is replaced by a substituent of the lowest priority (nitrogen atom), and thus the stereochemical notation does not change, i.e. 2 Rp affords 4a Rp or 3 Sp affords 4a Sp, even though these reactions occur with inversion of configuration at the phosphorus centre.
21. P = 8.4 ppm; ca. 10% after 20 min) was observed. In a separate experiment we showed that the addition of ethanethiol affected neither the stereochemical course of the halogen exchange reaction nor the subsequent reaction of the produced phosphorochloridate 3 with amines.
22. P = 3.28 ppm), from H-phosphonate 1 Sp. These findings substantiate the assumed inversion of configuration in the investigated halogen exchange reaction.