New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions

• Iveta Chena Tichá,
• Simona Hybelbauerová and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2019, 15, 830–839, doi:10.3762/bjoc.15.80

• evaluated in several enantioselective reactions, specifically in the asymmetric allylic amination (AAA), which showed a promising enantiomeric excess of up to 75% ee. Furthermore, a new disubstituted α-CD catalyst was prepared as a pure AD regioisomer and also tested in the AAA. Our results indicate that (i

• disubstituted CD derivatives performed similarly to monosubstituted CDs. Therefore, these new CD derivatives with cinchona alkaloids effectively catalyze asymmetric allylic aminations and have the potential to be successfully applied in other enantioselective reactions. Keywords: asymmetric allylic amination

• asymmetric allylic amination (AAA). We successfully prepared a series of monosubstituted α- and β-CDs derivatives with the cinchona alkaloids cinchonine, cinchonidine, quinine, and quinidine with up to 95% isolated yield through CuAAC click reactions. By this simple, high-yielding and quick method we

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

• ) are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with

• ], manganese- [19][20][21], iron- [23][24], copper- [22][31], rhenium- [26], and rhodium- [27] based reagents. The recent resurgence of interest in the nitroso–ene reaction builds on earlier work by Sharpless, Nicolas, Jørgensen and others. Sharpless reported allylic amination of 2-methyl-2-hexene with N-(p

• -chlorophenyl)hydroxylamine using a molybdenum complex [32], a process that was made catalytic by adding excess N-phenylhydroxylamine [33]. The combination of iron(II) phthalocyanines [34][35] or iron(II)/iron(III) chloride [36][37][38] and N-phenylhydroxylamine effect allylic amination reactions that are

Enantioselective synthesis of planar chiral ferrocenes via palladium-catalyzed annulation with diarylethynes

• Yan-Chao Shi,
• Rong-Fei Yang,
• De-Wei Gao and
• Shu-Li You

Beilstein J. Org. Chem. 2013, 9, 1891–1896, doi:10.3762/bjoc.9.222

• ). The allylic substitution reactions of (rac)-4 had been carried out. The allylic alkylation reaction proceeded in 95% yield and 44% ee (Scheme 3, reaction 1) and the allylic amination reaction proceeded in 32% yield and 43% ee (Scheme 3, reaction 2) [69][70][71]. Although only moderate

Synthesis of skeletally diverse alkaloid-like molecules: exploitation of metathesis substrates assembled from triplets of building blocks

• Sushil K. Maurya,
• Mark Dow,
• Stuart Warriner and
• Adam Nelson

Beilstein J. Org. Chem. 2013, 9, 775–785, doi:10.3762/bjoc.9.88

• with methyl chloroformate and DMAP. The allylic carbonate 15 underwent efficient asymmetric allylic amination [20] with o-nitrophenylsulfonamide as the nucleophile to give the allylic sulfonamide 17 in 66% yield; in addition, the linear product 16 was also obtained in 7% yield. Desilylation of 17 (→ 18

Titanium-mediated reductive cross-coupling reactions of imines with terminal alkynes: An efficient route for the synthesis of stereodefined allylic amines

• Kebin Mao,
• Guoqin Fan,
• Yuanhong Liu,
• Shi Li,
• Xu You and
• Dan Liu

Beilstein J. Org. Chem. 2013, 9, 621–627, doi:10.3762/bjoc.9.69

• ], iodocyclocarbamates [19] and isoxazolines [20]. Although it has been reported that allylic amines can be synthesized by methods such as amination of allylic alcohols [21][22][23][24], direct allylic amination of simple alkenes [25][26][27], Morita–Baylis–Hillman reaction [28], alkenylation of imines [29][30][31][32

Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins

• Hang Zhang,
• Shan-Jun Zhang,
• Qing-Qing Zhou,
• Lin Dong and
• Ying-Chun Chen

Beilstein J. Org. Chem. 2012, 8, 1241–1245, doi:10.3762/bjoc.8.139

• investigation of a Lewis base catalyzed asymmetric allylic amination of Morita–Baylis–Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee) and in high

• yields (up to 97%). Keywords: allylic amination; asymmetric organocatalysis; Morita–Baylis–Hillman carbonates; 2-oxindoles; quaternary chiral center; Introduction Chiral 3-amino-2-oxindoles are versatile and useful units for the preparation of natural products and drug candidates, such as the

• isatins to obtain 2-oxindoles bearing a C3-quaternary chiral center, by the catalysis of chiral tertiary amines, β-isocupreidine (β-ICD) or its derivatives [23][24]. We envisaged that such a catalytic strategy should be applicable to the allylic amination of the corresponding MBH carbonates [25][26][27

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• substituted pyrroles involving a dihalogeno substrate and a sequential Sonogashira coupling followed by an hydroamination was developed by Duchêne and Parrain [32]. In this one-pot sequence, the first reaction is an allylic amination between the 3,4-diiodobut-2-enoic acid (54) and a primary amine, which can

• –N allylic amination, followed by a Sonogashira cross-coupling and an intramolecular hydroamination furnished a dihydroexoalkylidene pyrrole 55, which rearranges into pyrrole 56. This Pd/Cu-mediated three-component approach is influenced by the nature of the nitrogen nucleophile, and the reaction

• partners through a Pd-mediated allylic amination The allene carbopalladation process with organic halides is known to generate a π-allylpalladium intermediate, which can be trapped by intermolecular carbo- or heteronucleophiles to produce the corresponding three-component adduct. This strategy was used by

Amine-linked diglycosides: Synthesis facilitated by the enhanced reactivity of allylic electrophiles, and glycosidase inhibition assays

• Ian Cumpstey,
• Jens Frigell,
• Elias Pershagen,
• Tashfeen Akhtar,
• Elena Moreno-Clavijo,
• Inmaculada Robina,
• Dominic S. Alonzi and
• Terry D. Butters

Beilstein J. Org. Chem. 2011, 7, 1115–1123, doi:10.3762/bjoc.7.128

• for transition-metal-catalysed allylic amination reactions [19][20][21] as a possible coupling method. We report our investigations into this area in this paper. There is extensive coverage in the literature of the derivatisation of primary carbohydrate alcohols by Mitsunobu type reactions [22

• ]. The palladium-catalysed allylic amination reaction on unsaturated pyranose rings was pioneered thirty years ago by Hanna and Baer [19][20], and has more recently been reinvestigated with rather simple nitrogen nucleophiles [30][31]. Carbohydrate amines have been used as nucleophiles in allylic

• , the trans relationship between the flanking NNsR and OEt groups effectively crowds both faces of the olefin, blocking its reactivity. We briefly examined palladium-catalysed allylic amination as a possible coupling procedure. The allylic alcohol in the threo derivative 2 was converted into its

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• aziridines 174 (Scheme 30) [80]. Chan’s group developed an efficient synthetic route to 1,2-dihydroquinolines 177 via AuCl3/AgSbF6-catalyzed intramolecular allylic amination of 2-(tosylamino)phenylprop-1-en-3-ols 176 (Scheme 31) [81]. The mechanism is suggested to involve activation of the alcohol substrate