Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• to both of the carbonyl oxygens. During the course of studying the addition of aromatic thiols to α,β-unsaturated benzamides and enones, Chen, Ding, and Wu first reported the conjugate addition of thiophenol (23) to N-methacryloyl benzamide 91 followed by enantioselective protonation using Takemoto’s

Cascade alkylarylation of substituted N-allylbenzamides for the construction of dihydroisoquinolin-1(2H)-ones and isoquinoline-1,3(2H,4H)-diones

• Ping Qian,
• Bingnan Du,
• Wei Jiao,
• Haibo Mei,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2016, 12, 301–308, doi:10.3762/bjoc.12.32

• examined, and a lower chemical yield was found when the reaction was performed at 100 °C (Table 1, entry 16). With the optimized conditions developed, we then carried out a substrate generality study using various types of N-(2-methylallyl)benzamides 4 to react with cyclohexane (2a). As shown in Scheme 2

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• related ring-fused products, the formation of other ring sized scaffolds such as five-membered structure were much less. An interesting cascade reaction between DG-functionalized benzamides 99 and malonates 100, which enabled the synthesis of indolinones 101 via selective C–C and C–N bond construction

• for lactam synthesis. Copper-catalyzed amidation/sulfonamidation of aryl C–H bonds. C–H amidation of pyridinylbenzenes and indoles. Mechanism of the Cu-catalyzed C2-amidation of indoles. Copper-catalyzed, 2-phenyl oxazole-assisted C–H amidation of benzamides. DG-assisted amidation/imidation of indole

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• functionalized 8-methylquinolinyl substrates reported by Sanford et al. [43], Daugulis and co-worker [44] established in 2013 a copper-catalyzed arene C–H o-fluorination of N-(quinolin-8-yl)benzamides 14. The mono- and/or difluorination took place in the presence of CuI, N-methylmorpholine N-oxide (NMO) and

• -catalyzed arene C–H fluorination of benzamides. Copper-catalyzed arene C–H iodination of 1,3-azoles. Copper-catalyzed C–H halogenations of phenols. Proposed mechanism for the C–H halogenation of phenols. Copper-catalyzed halogenation of electron enriched arenes. Copper-catalyzed C–H bromination of arenes

The facile construction of the phthalazin-1(2H)-one scaffold via copper-mediated C–H(sp²)/C–H(sp) coupling under mild conditions

• Wei Zhu,
• Bao Wang,
• Shengbin Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2015, 11, 1624–1631, doi:10.3762/bjoc.11.177

• , entry 19). In addition, single-crystal X-ray diffraction of 3a showed that the Z-isomer of the alkene is preferentially formed [24]. Next, the scope of 8-aminoquinoline benzamides and the generality of this process were investigated under the optimized conditions. As shown in Scheme 2, most of the

• examined substrates (1b–1m) provided the corresponding products (3b–3m) in moderate to good yields. Benzamides with weak electron-donating groups (–Me, –OCF3,) at the para-position were well compatible with good yields (3b, 3c), while the introduction of a methoxy group led to a slight decrease in the

• yield (3d). Electron-poor benzamides (–CF3, –COOMe) worked well under the transformation system and gave good yields (3e, 3f). Notably, halides and an ethenyl group were tolerated under the standard reaction conditions (3g–3i), which could undergo further elaboration. The C–H activation of meta

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• the selective replacement of one of the two hydrogen atoms in the ortho-position of acetanilide; the molar ratio of the C- and O-reagents is close to stoichiometric. The acetoxylation (product 42) and methoxylation (product 43) of N-(2-benzoylphenyl)benzamides 41 at the ortho-position of the benzamide

• moiety of the substrate were performed using Pd(OAc)2 combined with PhI(OAc)2 as the oxidant (Scheme 9) [58]. The alkoxylation of N-tosylbenzamides 44 in the presence of the same oxidative system takes place at room temperature and gives products 45 [59]. The reactions of benzamides containing the nitro

Synthesis of enantiomerically pure N-(2,3-dihydroxypropyl)arylamides via oxidative esterification

• Akula Raghunadh,
• Satish S More,
• T. Krishna Chaitanya,
• Yadla Sateesh Kumar,
• Suresh Babu Meruva,
• L. Vaikunta Rao and
• U. K. Syam Kumar

Beilstein J. Org. Chem. 2013, 9, 2129–2136, doi:10.3762/bjoc.9.250

• -dihydroxypropyl)benzamides (6a and 6b): To a solution of phthalimido hydroxyl ester (5a) (5 g, 0.016 mol) in dichloromethane (5 mL), methylamine (15 mL) was added at 25–30 °C and stirred for 2 h. Sodium hydroxide (0.64 g, 0.016 mol) was added, and the mixture was stirred for another 1–2 h. The reaction mixture

On the control of secondary carbanion structure utilising ligand effects during directed metallation

• Andrew E. H. Wheatley,
• Jonathan Clayden,
• Ian H. Hillier,
• Alison Campbell Smith,
• Mark A. Vincent,
• Laurence J. Taylor and
• Joanna Haywood

Beilstein J. Org. Chem. 2012, 8, 50–60, doi:10.3762/bjoc.8.5

• (L = PMDTA, DGME; DGME = diglyme) and also, under kinetic control, the remarkable hemi-solvated ortho-lithiate (Scheme 4). This development allowed thermodynamic lithiate 5-Lil·PMDTA to be successfully used to generate a variety of benzamides bearing quaternary C-centres at the aromatic 2-position

Directed aromatic functionalization in natural-product synthesis: Fredericamycin A, nothapodytine B, and topopyrones B and D

• Charles Dylan Turner and
• Marco A. Ciufolini

Beilstein J. Org. Chem. 2011, 7, 1475–1485, doi:10.3762/bjoc.7.171

• chlorinated benzamides undergo ortho-deprotonation without difficulty [104], implying that the resistance of 57 cannot be attributed to the chloro substituent per se. Nor can the problem be ascribed to sequestration of the base through coordination/chelation [33] effects involving the chlorine atom. Such a

Approaches towards the synthesis of 5-aminopyrazoles

• Ranjana Aggarwal,
• Vinod Kumar,
• Rajiv Kumar and
• Shiv P. Singh

Beilstein J. Org. Chem. 2011, 7, 179–197, doi:10.3762/bjoc.7.25

• catalyzed reaction of benzoylacetonitrile 51 and acetonitrile, yielded 5-amino-3-aryl-1H-pyrazoles 53. Corresponding amide derivatives, i.e., N-(1,3-diaryl-1H-pyrazol-5-yl)benzamides 54 were prepared by further treating aminopyrazoles 53 with substituted benzoyl chlorides in DCM (Scheme 13) [44]. 3

The enantiospecific synthesis of (+)-monomorine I using a 5-endo- trig cyclisation strategy

• Malcolm B. Berry,
• Donald Craig,
• Philip S. Jones and
• Gareth J. Rowlands

Beilstein J. Org. Chem. 2007, 3, No. 39, doi:10.1186/1860-5397-3-39

• optimisation obviated the need for chromatography following the protecting group exchange, and the benzamides 11 could be isolated in high purity and good yield. Hydroxyalkylation with a range of aldehydes proceeded without issue to give the β-hydroxysulfones 12 in excellent yields. The β-hydroxysulfones were