Facile C21functionalization through a novel functional group transfer reaction in 16α,17α-epoxy-3β-hydroxypregn-5-en-20-one and its applications

2002 ◽  
pp. 2102-2103 ◽  
Author(s):  
Navdeep K. Girdhar ◽  
Mohan Paul S. Ishar
Keyword(s):  
Transfer Reaction ◽  
Functional Group ◽  
Group Transfer

ChemInform Abstract: Homolytic Alkyl Group Transfer Reaction of Photoactivated Alkylcobaloximes into Thiols.

ChemInform ◽  
1989 ◽  
Vol 20 (5) ◽  
Author(s):  
M. KIJIMA ◽  
K. MIYAMORI ◽  
T. SATO
Keyword(s):  
Alkyl Group ◽  
Transfer Reaction ◽  
Group Transfer

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bipyridine cocrystal with their crystal structures

2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Transfer Reaction ◽  
Acyl Transfer ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Hydrogen Bonding Interactions ◽  
Benzoyl Group ◽  
The Stability ◽  
Group Migration

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

Pyridinium Salts as Redox‐Active Functional Group Transfer Reagents

2020 ◽  
Vol 59 (24) ◽  
pp. 9264-9280 ◽  
Author(s):  
Simon L. Rössler ◽  
Benson J. Jelier ◽  
Emmanuel Magnier ◽  
Guillaume Dagousset ◽  
Erick M. Carreira ◽  
...  
Keyword(s):  
Functional Group ◽  
Pyridinium Salts ◽  
Group Transfer ◽  
Active Functional Group ◽  
Redox Active

Dual-Face Nucleoside Scaffold Featuring a Stereogenic All-Carbon Quaternary Center. Intramolecular Silicon Tethered Group-Transfer Reaction

2014 ◽  
Vol 16 (21) ◽  
pp. 5698-5701 ◽  
Author(s):  
Guillaume Tambutet ◽  
Fabiola Becerril-Jiménez ◽  
Starr Dostie ◽  
Ryan Simard ◽  
Michel Prévost ◽  
...  
Keyword(s):  
Transfer Reaction ◽  
Group Transfer ◽  
Quaternary Center

Synthese und Photolyse von 5-Diazo-5-[13C] -homoadamantanon-(4).

1976 ◽  
Vol 31 (5) ◽  
pp. 586-588 ◽  
Author(s):  
Klaus-Peter Zeller
Keyword(s):  
Carboxylic Acid ◽  
Transfer Reaction ◽  
Uv Light ◽  
Intermediate Formation ◽  
Ring Expansion ◽  
Group Transfer ◽  
Total Absence ◽  
Adamantane Skeleton ◽  
Diazo Group

The synthesis of 5-diazo-5-[13C]-homoadamantan-4-one (12) is achieved by ring expansion of adamantanone with 13C-labelled diazomethane, conversion of the resulting 4-[13C]-homoadamantan-4-one (10) to the hydroxymethylene compound (11), followed by deformylative diazo group transfer reaction. The photolysis of 12 with pyrex filtered UV-light in dioxane-water (10:1) yields adamantan-2-carboxylic acid containing all the label in the 2-position of the adamantane skeleton. The total absence of isotope scrambling excludes the intermediate formation of the polycyclic oxiren (16) (Scheme 3).

scholarly journals Methyl Radical Initiated Kharasch and Related Reactions

2020 ◽  
Author(s):  
Nicholas Tappin ◽  
Philippe Renaud
Keyword(s):  
Halogen Atom ◽  
Functional Group ◽  
Chain Process ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Reaction Conditions ◽  
Alternative Source ◽  
Group Transfer ◽  
Radical Trap ◽  
Flash Column Chromatography

An improved procedure to run halogen atom and related chalcogen group transfer radical additions is reported. The procedure relies on the thermal decomposition of di-<i>tert</i>-butylhyponitrite (DTBHN), a safer alternative to the explosive diacetyl peroxide, to produce highly reactive methyl radicals that can initiate the chain process. This mode of initiation generates byproducts that are either gaseous (N<sub>2</sub>) or volatile (acetone and methyl halide) thereby facilitating greatly product purification by either flash column chromatography or distillation. In addition, remarkably simple and mild reaction conditions (refluxing EtOAc during 30 minutes under normal atmosphere) and a low excess of the radical precursor reagent (2.0 equivalents) make this protocol particularly attractive for preparative synthetic applications. This initiation procedure has been demonstrated with a broad scope since it works efficiently to add a range of electrophilic radicals generated from iodides, bromides, selenides and xanthates over a range of unactivated terminal alkenes. A diverse set of radical trap substrates exemplifies a broad functional group tolerance. Finally, di-<i>tert</i>-butyl peroxyoxalate (DTBPO) is also demonstrated as alternative source of <i>tert-</i>butoxyl radicals to initiate these reactions under identical conditions which gives gaseous byproducts (CO<sub>2</sub>).

Polymergebundenes Sulfonylazid zur entformylierenden Diazogruppen-Übertragung und zur Diazo -cyclopolyen -Synthese / Polymer Anchored Sulfonylazide for Deformylating Diazo Group Transfer and the Synthesis of Diazo-cyclopolyenes

1981 ◽  
Vol 36 (9) ◽  
pp. 1149-1152 ◽  
Author(s):  
Heinz Dürr ◽  
Gerhard Hauck ◽  
Wolfgang Brück ◽  
Helge Kober
Keyword(s):  
Low Temperature ◽  
Transfer Reaction ◽  
Diazo Compound ◽  
Alternative Route ◽  
Secondary Product ◽  
Group Transfer ◽  
Sulfonyl Azide ◽  
Polymer Anchored ◽  
Cyclic Polyenes ◽  
Diazo Group

AbstractPolymer anchored sulfonylazide is compared with its efficiency in the diazogroup transfer reaction of tosylazide. The resulting yields with the polymeric reaction are slightly lower than with tosylazide. However the greater thermostability of polymeric sulfonyl azide and its workup procedure make this alternative very attractive for synthesis. The reaction of polymeric sulfonyl azide with cyclic polyenes gives very small yields compared with the monomeric reaction. The attempt to generate diazocyclononatetraene by an alternative route leads only to the secondary product namely indene. At low temperature, and intermediate diazo-compound is, however, observed, which is tentatively assigned to structure 12.

Charge frustration in ligand design and functional group transfer

2021 ◽  
Author(s):  
Dominik Munz ◽  
Karsten Meyer
Keyword(s):  
Functional Group ◽  
Ligand Design ◽  
Group Transfer
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