107396-03-2

Upstream product

• 3975-77-7 1-bromo-2,4,6-tri-tert-butylbenzene 
• 31039-82-4 2-iodo-1,3,5-tri-tert-butylbenzene 
• 35383-91-6 2,4,6-tri-tert-butylphenyllithium 

Relevant academic research and scientific papers

Catalytic selective deuteration of halo(hetero)arenes

Deuterium labeled aromatic and heteroaromatic compounds are synthesized in good to excellent yields with >98% deuterium purity via palladium catalyzed deuterodehalogenation reaction using commercially available and inexpensive reagents. Selective deuteration of bromoaniline is also demonstrated without H/D exchange in an amino N-H group.

General and Practical Potassium Methoxide/Disilane-Mediated Dehalogenative Deuteration of (Hetero)Arylhalides

Herein we describe a general, mild and scalable method for deuterium incorporation by potassium methoxide/hexamethyldisilane-mediated dehalogenation of arylhalides. With CD3CN as a deuterium source, a wide array of heteroarenes prevalent in pharmaceuticals and bearing diverse functional groups are labeled with excellent deuterium incorporation (>60 examples). The ipso-selectivity of this method provides precise access to libraries of deuterated indoles and quinolines. The synthetic utility of our method has been demonstrated by the incorporation of deuterium into complex natural and drug-like compounds.

Method for preparing deuterated aromatic organic compound

The invention provides a method for preparing a deuterated aromatic organic compound. The method comprises the following steps: firstly, dissolving a halogenated aromatic compound and an alkali metal salt MA into a deuterated solvent or a mixed solvent of the deuterated solvent and a common solvent, dropping an organic silicon reagent, performing stirring reaction at minus 40 DEG C to 150 DEG C, and performing separation purification after reaction, thereby obtaining the deuterated aromatic organic compound. By adopting the method, the deuterated aromatic organic compound can be efficiently, economically and environment-friendly prepared without participation of a transition metal or a metallic tin reagent, and the deuteration rate of the prepared deuterated product is greater than 95%. The method is gentle in condition, good in substrate universality and high in yield, and the prepared deuterated compound can be widely applied to fields of medicine chemistry and organic chemistry.

Super-electron donors: Bis-pyridinylidene formation by base treatment of pyridinium salts

Deprotonation of bispyridinium salt 7b affords bispyridinylidene 10, a very powerful neutral organic two-electron donor [E1/2 (DMF) = -1.13 V vs Ag/AgCI/KCI (sat)], presumably via the pyridinylidene 8. Donor 10 reduces aryl iodides and bromides to aryl anions in excellent yield and also reductively cleaves selected phenylalkylsulfones very efficiently.

Reactions of 2,4,6-Tri-t-butylphenyllithium with Deuterated Formate, Thioformate and Selenoformate

O-Cholesteryl chalcogenoformates-d, DC(=X)(OR) (2: X=O; 3: X=S; 4: X=Se; R=3β-cholesteryl), were synthesized and allowed to react with 2,4,6-tri-t-butylphenyllithium. 1,3,5-Tri-t-butylbenzene was a main product in each reaction. The other products were 2,4,6-tri-t-butylbenzaldehyde-d (9) for 2, 2,4,6-tri-t-butylthiobenzaldehyde-d for 3, and 9, 6,8-di-t-butyl-1-deuterio-3,4-dihydro-4,4-dimethyl-1H-2-benzoselenin, bis(2,4,6-tri-t-butyl-α-deuteriobenzyl) diselenide, and bis(2,4,6-tri-t-butyl-α-deuteriobenzyl) triselenide for 4.The mechanisms for these reactions have been discussed.

Reactions of 2,4,6-Tri-t-butylphenyllithium with O-Alkyl Selenoformates: Intermediate Formation of 2,4,6-Tri-t-butylselenobenzaldehyde

2,4,6-Tri-t-butylphenyllithium reacts with O-alkyl selenoformates (1) at three different sites (i.e., the selenoformyl carbon, the selenoformyl hydrogen, and the selenium) to give 1,3,5-tri-t-butylbenzene, 2,4,6-tri-t-butylbenzaldehyde, 6,8-di-t-butyl-3,4-dihydro-4,4-dimethyl-1H-2-benzoselenin (11), bis(2,4,6-tri-t-butylphenylmethyl) di(and tri) selenides, bis(2,4,6-tri-t-butylphenyl) diselenide, and dibutyl diselenide depending on the reaction conditions and the alkyl group in 1.The formation of 11 is explained in terms of the intermediacy of 2,4,6-tri-t-butylselenobenzaldehyde, which is trapped by condensation rection with butylamine leading to N-(2,4,6-tri-t-butylbenzylidene)butylamine.Mechanism for the formation of these products is also discussed.