Organocatalytic asymmetric nitroso aldol reaction of α-substituted malonamates

• Ekta Gupta,
• Narendra Kumar Vaishanv,
• Sandeep Kumar,
• Raja Krishnan Purshottam,
• Ruchir Kant and
• Kishor Mohanan

Beilstein J. Org. Chem. 2022, 18, 217–224, doi:10.3762/bjoc.18.25

• using a silver-BINAP catalyst combination [25]. Later, the same group could successfully tune the catalytic system to control the regioselectivity in the addition of metal enolate to nitrosoarenes to achieve an α-hydroxyamination [26]. Since then, several groups have shown the use of metal-catalyzed

• hydroxyamination of oxindoles and β-ketoamides [49][50][51][52][53][54]. Recently, it has been shown that malonate derivatives such as malonate half thioesters and malonamides could be effectively used in various enantioselecive addition reactions [55][56][57][58][59][60]. In this context, Chen and co-workers

• (2a) in toluene at 25 °C. Pleasingly, the hydroxyamination reaction proceeded smoothly to give the nitroso aldol product 4a in 80% yield and 60% ee (Table 1, entry 1). The influence of temperature was evaluated subsequently, and the reaction conducted at 0 °C without altering other parameters gave a

Stereoselective synthesis and transformation of pinane-based 2-amino-1,3-diols

• Ákos Bajtel,
• Mounir Raji,
• Matti Haukka,
• Ferenc Fülöp and
• Zsolt Szakonyi

Beilstein J. Org. Chem. 2021, 17, 983–990, doi:10.3762/bjoc.17.80

• synthesize novel, cyclic potentially analogues of sphingosine, incorporating a lipophilic natural pinane skeleton, starting from commercially available monoterpene-based allylic alcohols via a stereoselective hydroxyamination in the presence of a potassium osmate(VI) catalyst. We also planned to explore the

• isopinocarveol prepared from α-pinene. Pinane-condensed or spiro-oxazolidin-2-ones were formed in three steps by a stereoselective hydroxyamination process. The relative stereochemistry of new compounds was determined by 2D NMR spectroscopic and X-ray techniques. The resulting primary and secondary 2-amino-1,3

Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism

• David Porter,
• Belinda M.-L. Poon and
• Peter J. Rutledge

Beilstein J. Org. Chem. 2015, 11, 2549–2556, doi:10.3762/bjoc.11.275

• -nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+)-(2R,2′R)-1,1′-bis(2-pyridylmethyl)-2,2′-bipyrrolidine ((R,R′)-PDP). Keywords: CH activation; hydroxyamination; iron catalysis; nitroso-ene; Introduction The selective functionalization of C–H bonds is an

• context there has been a renewed focus on the chemistry of acylnitroso species in recent times [12][13][14][15], in particular on α-hydroxyamination of carbonyl compounds via nitrosocarbonyl aldol reactions [16][17][18][19][20][21] and allylic hydroxyamination of alkenes via nitroso–ene reactions [22][23

• was produced in ~10% yield with either ligand; performing the reaction open to air lifted the yield of the allylic hydroxyamination product 9 as high as 40%, but also substantially increased yields of 10 and 11 (Table 1). Control experiments using just the metal salt or each of the ligands on their