- Catalytic Diastereo- and Enantioselective Fluoroamination of Alkenes
-
The stereoselective synthesis of syn-β-fluoroaziridine building blocks via chiral aryl iodide-catalyzed fluorination of allylic amines is reported. The method employs HF-pyridine as a nucleophilic fluoride source together with mCPBA as a stoichiometric oxidant, and affords access to arylethylamine derivatives featuring fluorine-containing stereocenters in high diastereo- and enantioselectivity. Catalyst-controlled diastereoselectivity in the fluorination of chiral allylic amines enabled the preparation of highly enantioenriched 1,3-difluoro-2-amines bearing three contiguous stereocenters. The enantioselective catalytic method was applied successfully to other classes of multifunctional alkene substrates to afford anti-β-fluoropyrrolidines, as well as a variety of 1,2-oxyfluorinated products.
- Mennie, Katrina M.,Banik, Steven M.,Reichert, Elaine C.,Jacobsen, Eric N.
-
supporting information
p. 4797 - 4802
(2018/04/17)
-
- Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of trans-1,2-Disubstituted Alkenes
-
The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging trans-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility of our method. A creative route for the synthesis of vernakalant and Enablex was also developed.
- Chen, Caiyou,Jin, Shicheng,Zhang, Zhefan,Wei, Biao,Wang, Heng,Zhang, Kai,Lv, Hui,Dong, Xiu-Qin,Zhang, Xumu
-
supporting information
p. 9017 - 9020
(2016/08/05)
-
- Substrate-directable heck reactions with arenediazonium salts. The regio- and stereoselective arylation of allylamine derivatives and applications in the synthesis of naftifine and abamines
-
The palladium-catalyzed, substrate-directable Heck-Matsuda reaction of allylamine derivatives with arenediazonium salts is reported. The reaction proceeds under mild conditions, with excellent regio- and stereochemical control as a function of coordinating groups present in the allylamine substrate. The distance between the olefin moiety and the car-bonylic system seems to play a key role regarding the regiocontrol. The method presents itself as robust, as simple to carry out, and with wide synthetic scope concerning the allylic substrates and the type of arenediazonium employed. The synthetic potential of the method is illustrated by the short total syntheses of the bioactive compounds naftifine, abamine, and abamine SG.
- Prediger, Patricia,Barbosa, Lais Ferreira,Genisson, Yves,Correia, Carlos Roque Duarte
-
p. 7737 - 7749
(2011/12/01)
-