Influence of the trimethylsilyl group on the diastereoselectivity of an adjacent Claisen amide-acetal rearrangement

1983 ◽  
pp. 285 ◽  
Author(s):  
Eward H. Smith ◽  
Nicholas D. Tyrrell
Keyword(s):  
Trimethylsilyl Group ◽  
Amide Acetal

Catalytic activity of rhodium(I) complexes containing (ω-trimethylsilylalkyl)diphenylphosphines

1980 ◽  
Vol 45 (8) ◽  
pp. 2219-2223 ◽  
Author(s):  
Marie Jakoubková ◽  
Martin Čapka
Keyword(s):  
Catalytic Activity ◽  
Nmr Spectroscopy ◽  
Ir Spectroscopy ◽  
Electron Density ◽  
Phosphorus Atom ◽  
Proton Acceptor ◽  
Trimethylsilyl Group ◽  
Kinetics Of

Kinetics of homogenous hydrogenation of 1-heptene catalysed by rhodium(I) complexes prepared in situ from μ,μ'-dichloro-bis(cyclooctenerhodium) and phosphines of the type RP(C6H5)2 (R = -CH3, -(CH2)nSi(CH3)3; n = 1-4) have been studied. The substitution of the ligands by the trimethylsilyl group was found to increase significantly the catalytic activity of the complexes. The results are discussed in relation to the electron density on the phosphorus atom determined by 31P NMR spectroscopy and to its proton acceptor ability determined by IR spectroscopy.

scholarly journals Fullerene C60 promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary N-alkylbenzylamines

RSC Advances ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 5914-5922
Author(s):  
Suk Hyun Lim ◽  
Hannara Jang ◽  
Dae Won Cho
Keyword(s):  
Fullerene C60 ◽  
Dimethyl Acetylenedicarboxylate ◽  
Trimethylsilyl Group

C60-promoted photoaddition reactions of N-α-trimethylsilyl-N-alkylbenzylamines with dimethyl acetylenedicarboxylate (DMAD) were carried out.

scholarly journals Concatenated Batch and Continuous Flow Procedures for the Upgrading of Glycerol-Derived Aminodiols via N-Acetylation and Acetalization Reactions

Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 21
Author(s):  
Davide Rigo ◽  
Nadia Alessandra Carmo Dos Santos ◽  
Alvise Perosa ◽  
Maurizio Selva
Keyword(s):  
Continuous Flow ◽  
Solid Acid ◽  
Solid Acid Catalyst ◽  
Acid Catalyst ◽  
Catalyst Free ◽  
Amide Derivatives ◽  
Amide Acetal ◽  
Enol Ester ◽  
Isopropenyl Acetate

An unprecedented two-step sequence was designed by combining batch and continuous flow (CF) protocols for the upgrading of two aminodiol regioisomers derived from glycerol, i.e., 3-amino-1,2-propanediol and 2-amino-1,3-propanediol (serinol). Under batch conditions, at 80–90 °C, both substrates were quantitatively converted into the corresponding amides through a catalyst-free N-acetylation reaction mediated by an innocuous enol ester as isopropenyl acetate (iPAc). Thereafter, at 30–100 °C and 1–10 atm, the amide derivatives underwent a selective CF-acetalisation in the presence of acetone and a solid acid catalyst, to afford the double-functionalized (amide-acetal) products.

The role of trimethylsilyl group in highly stereoselective eposidation of allylic alcohols

1982 ◽  
Vol 23 (33) ◽  
pp. 3387-3390 ◽  
Author(s):  
Hiroki Tomioka ◽  
Toshifumi Suzuki ◽  
Koichiro Oshima ◽  
Hitosi Nozaki
Keyword(s):  
Allylic Alcohols ◽  
Trimethylsilyl Group

ChemInform Abstract: A Chemoselective, Acid-Mediated Conversion of Amide Acetal to Oxazole: The Key Step in the Synthesis of Cardiovascular Drug, Ifetroban Sodium.

ChemInform ◽  
2010 ◽  
Vol 29 (39) ◽  
pp. no-no
Author(s):  
S. SWAMINATHAN ◽  
A. K. SINGH ◽  
W.-S. LI ◽  
J. J. VENIT ◽  
K. J. JUN. NATALIE ◽  
...  
Keyword(s):  
Cardiovascular Drug ◽  
Amide Acetal

Synthesis of 2-Methylpyrrolo[1,2-a]pyrazin-1(2h)-one

1988 ◽  
Vol 41 (10) ◽  
pp. 1583 ◽  
Author(s):  
MA Brimble ◽  
MT Brimble ◽  
R Hodges ◽  
GA Lane
Keyword(s):  
Lewis Acid ◽  
Feeding Deterrent ◽  
Insect Feeding ◽  
Amide Acetal

The synthesis of 2-methylpyrrolo[1,2-a]pyrazin-1(2H)-one (2) present in the insect feeding deterrent peramine (1) through oxidation of the saturated lactam (3) is described. The preparation of the related 6- methyl-1H-pyrrolo[2,3-c]pyridin-7(6H)-one (12) through a Lewis-acid- catalysed cyclization of the amide acetal (7) is also described.

Studies Directed Towards the Total Synthesis of Anticapsin and Related Compounds. IV. Competitive Reaction of Amino and Carboxy Substituents in the Halohydrination of 2-Aminobicyclo[2.2.2]oct-5-ene-2-carboxylic Acid Derivatives

1994 ◽  
Vol 47 (12) ◽  
pp. 2221 ◽  
Author(s):  
MJ Crossley ◽  
SR Davies ◽  
TW Hambley
Keyword(s):  
Total Synthesis ◽  
The Other ◽  
X Ray Diffraction ◽  
Amino Groups ◽  
Competitive Reaction ◽  
Trimethylsilyl Group ◽  
X Ray ◽  
Tricyclic Compounds ◽  
Tricyclic Compound ◽  
Related Compounds

Bromohydrination of benzyl (1RS,2SR,4SR)-2-benzyloxycarbonylamino-1-trimethylsilyloxy-bicyclo[2.2.2]oct-5-ene-2-carboxylate (6a) and the (1RS,2RS,4SR)- diastereomer (6b) with N- bromoacetamide in aqueous dioxan has been investigated. These reactions are highly regio-and stereo-selective and give the corresponding bromohydrins (9a) and (9b), but in moderate to low yield. These bromohydrins have the necessary stereochemistry for conversion into anticapsin. The other products from the reaction are tricyclic compounds formed by capture of the anti- bromonium cation intermediates or resultant bromohydrins by interaction with the proximal protected carboxy and amino groups within the molecules. Thus the carbolactone (11) is formed from the endo -adduct (6a), and the carbonimidic acid derivative (12) and the cyclic urethane (13) are formed from the exo-adduct (6b). Cleavage of the trimethylsilyl group from the tricyclic compound (12) gives benzyl (1RS,2RS,3RS,7RS,8RS)-5-benzyloxy-2-bromo-8-hydroxy-4-oxa-6-azatricyclo[5.3.1.03,8]undec-5-ene-7-carboxylate(14), the structure of which was determined by X-ray diffraction methods and refined to a residual of 0.035 for 1549 independent observed reflections. The crystals of (14) are monoclinic, P21/c, a 12.954(3), b 6.197(3), c 26.784(7) Ǻ, β 95.33(2)°, Z 4. Reactions attempting to generate iodohydrins from the alkenes (6) were also highly regioselective and gave detrimethylsilylated iodo analogues of (11) and (13).

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