scholarly journals Synthesis of Enantiomerically Pure N-Boc-Protected 1,2,3-Triaminopropylphosphonates and 1,2-Diamino-3-Hydroxypropylphosphonates

Molecules ◽  
2019 ◽  
Vol 24 (21) ◽  
pp. 3857
Author(s):  
Aleksandra Trocha ◽  
Dorota G. Piotrowska ◽  
Iwona E. Głowacka
Keyword(s):  
Acetic Acid ◽  
Aziridine Ring ◽  
Enantiomerically Pure ◽  
Tert Butyl ◽  
Trimethylsilyl Azide

All possible isomers of 1,2,3-tri(N-tert-butoxycarbonylamino)propylphosphonate 6 were synthesized from the respective diethyl [N-(1-phenylethyl)]-1-benzylamino-2,3-epiiminopropylphosphonates 5 via opening the aziridine ring with trimethylsilyl azide (TMSN3) followed by hydrogenolysis in the presence of di-tert-butyl dicarbonate (Boc2O). [N-(1-phenylethyl)]-1-benzylamino-2,3-epiiminopropylphosphonates (1R,2R,1′S)-5a and (1S,2S,1′R)-5c were smoothly transformed into diethyl 3-acetoxy-1-benzylamino-2-[N-(1-phenylethyl)amino]propylphosphonates (1R,2R,1′S)-9a and (1S,2S,1′R)-9c, respectively by the opening of the aziridine ring with acetic acid. Transformations of [N-(1-phenylethyl)]-1-benzylamino-2,3-epiiminopropylphosphonates (1S,2R,1′S)-5b and (1R,2S,1′R)-5d into diethyl 3-acetoxy-1-benzylamino-2-[(1-phenylethyl)amino]propylphosphonates (1S,2R,1′S)-9b and (1R,2S,1′R)-9d were accompanied by the formation of ethyl {1-(N-benzylacetamido)-3-hydroxy-2-[(1-phenylethyl)amino]propyl}phosphonate (1S,2R,1′S)-10b and (1R,2S,1′R)-10d and 3-(N-benzylacetamido)-4-[N-(1-phenylethyl)]amino-1,2-oxaphospholane (3S,4R,1′S)-11b and (3R,4S,1′R)-11d as side products. Diethyl (1R,2R)-, (1S,2S)-, (1S,2R)- and (1R,2S)-3-acetoxy-1,2-di(N-tert-butoxycarbonylamino)propylphosphonates 7a–7d were obtained from the respective 3-acetoxy-1-benzylamino-2-[N-(1-phenylethyl)amino]propylphosphonates 9a–9d by hydrogenolysis in the presence of Boc2O.

scholarly journals Correction to Synthesis of Enantiomerically Pure 6-Substituted-Piperazine-2-Acetic Acid Esters as Intermediates for Library Production

2019 ◽  
Vol 84 (7) ◽  
pp. 4575-4575 ◽  
Author(s):  
Srinivas Chamakuri ◽  
Prashi Jain ◽  
Shiva Reddy Krishna Guduru ◽  
J. Winston Arney ◽  
Kevin R. MacKenzie ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Enantiomerically Pure ◽  
Substituted Piperazine ◽  
Acetic Acid Esters ◽  
Acid Esters

ChemInform Abstract: ACTION OF DIAZOMETHANE ON 2,6-DI-TERT-BUTYL-1,4-BENZOQUINONE DIAZIDE AS A NEW WAY OF CONSTRUCTING AN AZIRIDINE RING

1977 ◽  
Vol 8 (5) ◽  
pp. no-no
Author(s):  
G. F. BANNIKOV ◽  
M. G. LUCHINSKAYA ◽  
G. A. NIKIFOROV ◽  
V. V. ERSHOV
Keyword(s):  
Aziridine Ring ◽  
Tert Butyl

scholarly journals A cocrystal of two MoVIcomplexes bearing different diastereomers of the 2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolate ligand derived from (+)-ephedrine

2013 ◽  
Vol 69 (5) ◽  
pp. 509-512 ◽  
Author(s):  
Reijo Sillanpää ◽  
Mikko M. Hänninen
Keyword(s):  
Hydrogen Bonds ◽  
Octahedral Coordination ◽  
Molybdenum Complex ◽  
Enantiomerically Pure ◽  
One Dimensional ◽  
Π Interactions ◽  
Tert Butyl ◽  
Distorted Octahedral Coordination ◽  
Distorted Octahedral ◽  
Phenyl Rings

The title cocrystal contains two chiral conformational diastereomers,viz.(1S,2R,RN)- and (1S,2R,SN)-, of [2,4-di-tert-butyl-6-{[(1-oxido-1-phenylpropan-2-yl)(methyl)amino]methyl}phenolato](methanol)-cis-dioxidomolybdenum(VI), [Mo(C25H35NO2)O2(CH3OH)], representing the first example of a structurally characterized molybdenum complex with enantiomerically pure ephedrine derivative ligands. The MoVIcations exhibit differently distorted octahedral coordination environments, with two oxide ligands positionedcisto each other. The remainder of the coordination comprises phenoxide, alkoxide and methanol O atoms, with an amine N atom completing the octahedron. The distinct complexes are linked by strong intermolecular O—H...O hydrogen bonds, resulting in one-dimensional molecular chains. Furthermore, the phenyl rings are involved in weak T-shaped/edge-to-face π–π interactions with each other.

Nitration of 4-tert-butyl-o-xylene in acetic anhydride. Formation and rearomatization of adducts

1978 ◽  
Vol 56 (2) ◽  
pp. 258-266 ◽  
Author(s):  
Alfred Fischer ◽  
Khay Chuan Teo
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Nitro Group ◽  
Tert Butyl ◽  
Acidic Conditions ◽  
Group Migration

Nitration of 4-tert-butyl-1,2-dimethylbenzene in acetic anhydride gives trans-1-tert-butyl-3,4-dimethyl-4-nitro-1,4-dihydrophenyl acetate (6), trans-1-tert-butyl-3,4-dimethyl-4-nitro-1,4-dihydrophenol, 2-tert-butyl-4,5-dimethylphenyl acetate, 5-tert-butyl-2-methylbenzaldehyde, 4-tert-buty]-1,2-dimethyl-5-nitrobenzene, and 4-tert-butyl-1,2-dimethyl-6-nitrobenzene. 2-tert-Butyl-4,5-dimethylphenyl acetate and 3,4-dimethylphenyl acetate are the major products of solvolysis of 6 in moist acetic acid. Both of these compounds are likely formed via the cation generated by ionization of the nitro group. Under more acidic conditions 5-tert-butyl-2-methylbenzaldehyde and 4-tert-butyl-1,2-dimethyl-6-nitrobenzene, formed via the cation generated by acid-catalysed loss of acetate, become dominant, the balance between these products being controlled by the basicity of the solvent. More basic solvents deprotonate the cation to a triene, a key step in the formation of the aldehyde, at a competitive rate with the nitro group migration.

The bromination and chlorination of 2,3-dialkylindoles. Isolation of 3-bromo- and 3-chloro-2,3-dialkylindolenines and acid catalyzed conversion to 3-methoxyindolenines

1980 ◽  
Vol 58 (8) ◽  
pp. 808-814 ◽  
Author(s):  
Gary I. Dmitrienko ◽  
Edward A. Gross ◽  
Susan F. Vice
Keyword(s):  
Acetic Acid ◽  
Good Yield ◽  
Room Temperature ◽  
Chemical Properties ◽  
Nitrogen Atmosphere ◽  
Crystalline Solid ◽  
Tert Butyl ◽  
Acidic Conditions ◽  
Acid Catalyzed

The bromination of 2,3-dimethylindole in acetic acid followed by hydrolysis has been shown to yield the known dimer 16 of 3-hydroxy-2,3-dimethylindolenine 15 and not 3-hydroxymethyl-2-methylindole 12 as reported previously by others. Bromination of 2,3-dimethylindole in the presence of triethylamine has yielded 3-bromo-2,3-dimethylindolenine 17 as a crystalline solid which is stable at room temperature in a nitrogen atmosphere in the presence of triethylamine but decomposes vigorously in the absence of base. Under mildly acidic conditions 17 reacts rapidly with methanol to yield 3-methoxy-2,3-dimethylindolenine 3 in good yield. With tert-butyl hypochlorite in the presence of triethylamine, 2,3-dimethylindole gives 3-chloro-2,3-dimethylindolenine 2 which has chemical properties similar to 17 reacting readily with methanol to give 3. Similarly tetrahydrocarbazole was converted to the analogous chloroindolenine 5 and bromoindolenine 18 both of which readily underwent methanolysis to give 6 in good yield. A mechanism for the acid catalyzed methanolysis of 3-chloro- and 3-bromoindolenines is proposed.

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