Abstract:The copper-catalyzed and iodosylbenzene-mediated aziridination of (S)-N-(9-phenylfluorenyl)allylglycine tert-butyl ester 10 led to the isolation of the corresponding aziridine 13 in 28% yield (65% based on consumed starting material). The (2S,4S) isomer was preferentially formed with a diastereomeric excess of 36%.
“…An even better preparation of the nitrene precursors 76 was realized in “one pot” from sulfonamides and iodosylbenzene . This protocol was tested on the reaction of styrene catalyzed by [( S )- 2 /CuOTf] 111 with yield and enantioselectivity comparable to those described previously, but when it was applied to the aziridination of tert -butyl-( R )- N -(9-phenyl-9 H -fluoren-9-yl)allylglycinate, yield and diastereoselectivity were somewhat unsatisfactory. , …”
“…An even better preparation of the nitrene precursors 76 was realized in “one pot” from sulfonamides and iodosylbenzene . This protocol was tested on the reaction of styrene catalyzed by [( S )- 2 /CuOTf] 111 with yield and enantioselectivity comparable to those described previously, but when it was applied to the aziridination of tert -butyl-( R )- N -(9-phenyl-9 H -fluoren-9-yl)allylglycinate, yield and diastereoselectivity were somewhat unsatisfactory. , …”
“…6 Moreover, this reagent can be used in iminations reaction, 7 synthesis of azamacrocycles, 8 aza-Baylis-Hillman reaction, 9,10 synthesis of the aziridines 11,12 and important biologically compounds. 12,13 The reagent is commercially available as a white solid (mp 86-89 °C). 4 It should be used with carefull precaution, because it can be irritating to the eyes, the skin and the respiratory system.…”
Section: Methodsmentioning
confidence: 99%
“…12 Moreover, the comercial availability of easy-to-handle copper(II) complexes as catalyst makes this reaction highly practical. [11][12][13] (F) Wang et al used SES-NH 2 in a stage to the synthesis of an Nlinked glycopeptide presenting the H-type 2 human blood group determinant. The iodosulfonamidation was followed by thiolysis and release of iodide, providing a thioglycoside at room temperature in 85% yield.…”
“…This method was also used for the aziridination of steroids, such as 11-pregnene-3,20-dione, to develop the synthesis of aziridinyl or amino steroids. The Dodd group used this method for the synthesis of Enduracididine, a marine amino acid. , …”
Section: 3 (N-ses−imino) Phenyliodinane or Sesniph
Reagent331 Synthe...mentioning
group will be studied before presenting polymer-supported SES groups.
SES−Cl in Synthesis
Synthesis of Sulfonyl ChlorideThe free-radical addition 1 (Scheme 2) of sodium bisulfite on the double bond of vinyltrimethylsilane 1 catalyzed by tert-butyl perbenzoate provided the sulfonate salt 2 which is currently commercially available. This compound was directly transformed into sulfonyl chloride 3 (SES-Cl) by the action of phosphorus pentachloride, 1 thionyl chloride, 6 or sulfuryl chloride. 7 SES-Cl is a distillable liquid (bp ) 60°C/0.1 mmHg) which can be stored at room temperature.
Protection of AminesThe formation of sulfonamide 4 is usually carried out at low temperatures by reaction of the amine with an excess of SES-Cl 3 in the presence of triethylamine (eq 2, Table 1). In the case of aromatic or heterocyclic amines, sodium hydride is instead used as a base.The simple and general synthesis of N-SES amino acids 25,26 should be noted: it starts from the corresponding salt using a temporary trimethylsilane protection on the carboxylic acid function, followed by reaction with SES-Cl (Scheme 3).
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