Palladium-catalyzed substitution of (coumarinyl)methyl acetates with C-, N-, and S-nucleophiles

• Kalicharan Chattopadhyay,
• Erik Fenster,
• Alexander J. Grenning and
• Jon A. Tunge

Beilstein J. Org. Chem. 2012, 8, 1200–1207, doi:10.3762/bjoc.8.133

• possess interesting biological activity, the scope of the amination was investigated in somewhat more detail. Regarding the scope of the amine and coumarinyl acetate coupling reaction, dialkyl (5a–c) and the cyclic amines pyrrolidine (5d–5f), pyrazine (5g), and morpholine (5h) were competent coupling

Two-directional synthesis as a tool for diversity-oriented synthesis: Synthesis of alkaloid scaffolds

• Kieron M. G. O’Connell,
• Monica Díaz-Gavilán,
• Warren R. J. D. Galloway and
• David R. Spring

Beilstein J. Org. Chem. 2012, 8, 850–860, doi:10.3762/bjoc.8.95

• conditions, this time by using two equiv of AlCl3 in dichloromethane at room temperature. For monoester 20, only a single conjugate addition was possible, leaving the pendant terminal alkene groups as handles for further reactivity. This cyclisation proceeded to give the expected, functionalised morpholine

• speculate that the relative difficulty in the reaction is due to the reduced availability of the lone pair of the morpholine nitrogen compared to the piperidine nitrogen (pKa 8.36 versus 11.22) [31], retarding the rate of nucleophilic attack. Another possibility is that the oxygens in the pendant chains can

Synthesis and characterization of Sant-75 derivatives as Hedgehog-pathway inhibitors

• Chao Che,
• Song Li,
• Bo Yang,
• Shengchang Xin,
• Zhixiong Yu,
• Taofeng Shao,
• Chuanye Tao,
• Shuo Lin and
• Zhen Yang

Beilstein J. Org. Chem. 2012, 8, 841–849, doi:10.3762/bjoc.8.94

• heterocycles (motif C) and the position of the nitrogen atom in pyridine. As shown in Scheme 6, para-substituted pyridine was first replaced with meta- and ortho-pyridine, and other heterocycles, including pyrimidines and five-membered heteroaryl rings, as well as nonaromatic heterocycles, such as morpholine

An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

• Marcus Baumann,
• Ian R. Baxendale,
• Steven V. Ley and
• Nikzad Nikbin

Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57

• the morpholine derived enamine 245 was used the desired 1,3,5-substituted pyrazole was formed with 100% regioselectivity (Scheme 49). This high regioselectivity is only obtained when a 1,1-disubstituted enamine is used, the corresponding 1,2-disubstituted enamine yields mainly the other regioisomer

Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

• Carolin Fischer and
• Burkhard Koenig

Beilstein J. Org. Chem. 2011, 7, 59–74, doi:10.3762/bjoc.7.10

• to good yields of 49 and 50. Secondary acyclic amines 48 were unreactive: A variety of different conditions were investigated including the variation of base, ligand and copper source. Scheme 10 shows the optimized conditions for coupling with morpholine (46) and 2-(2-methoxyethoxy)ethanamine (47

9,10-Dioxa-1,2-diaza-anthracene derivatives from tetrafluoropyridazine

• Graham Pattison,
• Graham Sandford,
• Dmitrii S. Yufit,
• Judith A. K. Howard,
• John A. Christopher and
• David D. Miller

Beilstein J. Org. Chem. 2010, 6, No. 45, doi:10.3762/bjoc.6.45

• (EI+) m/z: 222 ([M]+, 10%), 138 (43), 74 (66), 63 (67), 50 (100). Reaction of 3,4-difluoro-9,10-dioxa-1,2-diaza-anthracene (5) with morpholine 3-Fluoro-4-(morpholin-4-yl)-9,10-dioxa-1,2-diaza-anthracene (9a) A mixture of 3,4-difluoro-9,10-dioxa-1,2-diaza-anthracene (5) (0.20 g, 0.90 mmol), morpholine

Comparison of zwitterionic N-alkylaminomethanesulfonic acids to related compounds in the Good buffer series

• Robert D. Long,
• Newton P. Hilliard Jr,
• Suneel A. Chhatre,
• Tatiana V. Timofeeva,
• Andrey A. Yakovenko,
• Daniel K. Dei and
• Enoch A. Mensah

Beilstein J. Org. Chem. 2010, 6, No. 31, doi:10.3762/bjoc.6.31

• aminomethanesulfonates, so our initial efforts were to synthesize the initial target compound N-morpholinomethanesulfonic acid (MMS) (1) by the reaction of morpholine with chloromethanesulfonic acid (Scheme 2). In spite of numerous attempts, this route produced no product, however. A subsequent literature search

• ) is readily available from commercial sources and reacts in good yield with morpholine in aqueous solution over several days at room temperature, or in hours with moderate heating, to form the desired product 1 in a zwitterionic or salt form (depending on the workup conditions). We extended this

• . alcohols (i.e. methanol, ethanol), as the materials are insoluble in other solvents. N-Morpholinomethanesulfonic acid [MMS (or MoMS)] (1). This was prepared as the half sodium salt by the general procedure from 0.200 mol of morpholine (17.4 mL), yielding 31.6 g (0.164 mol) of 1 (82% isolated yield) as a

2-Phenyl- tetrahydropyrimidine- 4(1H)-ones – cyclic benzaldehyde aminals as precursors for functionalised β²-amino acids

• Markus Nahrwold,
• Arvydas Stončius,
• Anna Penner,
• Beate Neumann,
• Hans-Georg Stammler and
• Norbert Sewald

Beilstein J. Org. Chem. 2009, 5, No. 43, doi:10.3762/bjoc.5.43

• ) Boc2O, DMAP, CH3CN, 16 h, rt; b) 1. n-BuLi, THF, −78 °C, 30 min; 2. Cbz-Cl, rt, 16 h; c) H2, 10% Pd/C, abs. THF, 4 h, rt. Synthesis of enantiopure 2-phenyl-tetrahydropyrimidine-4(1H)-ones. a) PhCH(OMe)2, BF3·Et2O (6.0 equiv), CH2Cl2, −30 °C → −15 °C, 16 h; b) 1. [Pd(PPh3)4], morpholine, THF, rt, 1 h; 2

The tert- amino effect in heterocyclic chemistry: Synthesis of new fused pyrazolinoquinolizine and 1,4-oxazinopyrazoline derivatives

• Dipak Prajapati and
• Kalyan Jyoti Borah

Beilstein J. Org. Chem. 2007, 3, No. 43, doi:10.1186/1860-5397-3-43

• pyrazolone 1 under Vilsmeier conditions.[28] The 5-chloro atom of 2 is readily displaced by nucleophiles [29][30][31] and hence the reaction with several cyclic sec-amines (viz pyrrolidine, piperidine and morpholine) resulted in smooth conversion to the 5-tert-amino derivatives 3. These were then used in the

• characterized fully by high resolution spectral analysis (see Supporting Information File 1 &Supporting Information File 2 for full experimental and spectral data). We then reacted chloroformyl pyrazoline 2 with pyrrolidine and morpholine to get the corresponding tert-amino derivatives 3. The olefinic products

Synthesis of sulfonimidamides from sulfinamides by oxidation with N-chlorosuccinimide

• Olga García Mancheño and
• Carsten Bolm

Beilstein J. Org. Chem. 2007, 3, No. 25, doi:10.1186/1860-5397-3-25

• ] were tested as well (Table 1, Entries 8–10), but they exhibited a significantly lower efficiency than the previous chlorinating agents. Since N-chlorosuccinimide (NCS) had been applied for the oxidation of 4-(methylthio)morpholine towards the synthesis of diazasulfonium salts[22] and the preparation of

Stereoselective α-fluoroamide and α-fluoro- γ-lactone synthesis by an asymmetric zwitterionic aza-Claisen rearrangement

• Kenny Tenza,
• Julian S. Northen,
• David O'Hagan and
• Alexandra M. Z. Slawin

Beilstein J. Org. Chem. 2005, 1, No. 13, doi:10.1186/1860-5397-1-13

• phenylglycine as previously described.[20] In the first instance a Yb(OTf)3 mediated aza-Claisen rearrangement using allyl morpholine 10 and acid chloride 9 was explored following MacMillan's protocol.[21] This proceeded smoothly to give the α-fluoroamide 11 in good yield although reduction of the equivalence