Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

• Thilo Focken and
• Stephen Hanessian

Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195

Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilyl)methyl)aniline with cyclic α,β-unsaturated carbonyl compounds

• Dominik Lenhart and
• Thorsten Bach

Beilstein J. Org. Chem. 2014, 10, 890–896, doi:10.3762/bjoc.10.86

• -induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH) or 1.0 mol % (in CH2Cl2) [Ir(ppy)2(dtbbpy)]BF4 as the catalyst. Two

• reactions to other cyclic α,β-unsaturated carbonyl compounds. In particular, we were interested to see whether cyclization reactions as for product 4 would be observed when using α,β-unsaturated lactones and lactams in combination with a silylated amine and an iridium catalyst. In this article, we provide

• 7 operates [54][55][56][57][58]. Oxidation of the aniline and loss of the trimethylsilyl group leads to an α-aminomethyl radical, which adds to the cyclic α,β-unsaturated carbonyl compound (Scheme 8). The intermediate radical A can undergo immediate reduction presumably by concomitant oxidation of

An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

• Marcus Baumann and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2013, 9, 2265–2319, doi:10.3762/bjoc.9.265

• derivatives are treated with α,β-unsaturated carbonyl compounds in the presence of ammonia to initially form dihydropyridines 1.38, which can ultimately be converted into the corresponding aromatic pyridine upon oxidation with a variety of oxidants such as MnO2, HNO2, HNO3 or cerium ammonium nitrate (CAN

Elucidation of the regio- and chemoselectivity of enzymatic allylic oxidations with Pleurotus sapidus – conversion of selected spirocyclic terpenoids and computational analysis

• Verena Weidmann,
• Mathias Schaffrath,
• Holger Zorn,
• Julia Rehbein and
• Wolfgang Maison

Beilstein J. Org. Chem. 2013, 9, 2233–2241, doi:10.3762/bjoc.9.262

• ] or α,β-unsaturated carbonyl compounds are attractive synthetic targets of high economic and scientific interest [11][12][13][14][15][16][17]. Allylic oxidations of olefins to enones have classically been performed with strong oxidants such as chromium or other metal-based reagents [18][19]. In

AgOTf-catalyzed one-pot reactions of 2-alkynylbenzaldoximes with α,β-unsaturated carbonyl compounds

• Qiuping Ding,
• Dan Wang,
• Puying Luo,
• Meiling Liu,
• Shouzhi Pu and
• Liyun Zhou

Beilstein J. Org. Chem. 2013, 9, 1949–1956, doi:10.3762/bjoc.9.231

• various α,β-unsaturated carbonyl compounds under mild conditions are described, which provides a facile and efficient pathway for the synthesis of 1-alkylated isoquinoline derivatives. The method tolerates a wide range of substrates and allows for the preparation of the products of interest in moderate to

• excellent yields. Keywords: 2-alkynylbenzaldoxime; cyclization; 2-(isoquinolin-1-yl)ethanol; rearrangement; α,β-unsaturated carbonyl compound; Introduction One-pot combinations of multi-catalysis and multi-component cascade reactions [1][2][3][4][5][6], in which several bond-forming steps take place in a

• progress in this aspect. Wu and co-workers described an efficient three-component reaction of a 2-alkynylbenzaldoxime and an α,β-unsaturated carbonyl compound with bromine or iodine monochloride under mild conditions, which generates the 1-alkylated isoquinolines in good to excellent yields [36]. Wu and co

Raman spectroscopy as a tool for monitoring mesoscale continuous-flow organic synthesis: Equipment interface and assessment in four medicinally-relevant reactions

• Trevor A. Hamlin and
• Nicholas E. Leadbeater

Beilstein J. Org. Chem. 2013, 9, 1843–1852, doi:10.3762/bjoc.9.215

• is assessed by studying four reactions, all involving formation of products bearing α,β-unsaturated carbonyl moieties; synthesis of 3-acetylcoumarin, Knoevenagel and Claisen–Schmidt condensations, and a Biginelli reaction. In each case it is possible to monitor the reactions and also in one case, by

• means of a calibration curve, determine product conversion from Raman spectral data as corroborated by data obtained using NMR spectroscopy. Keywords: flow processing; Raman spectroscopy; reaction monitoring; α,β-unsaturated carbonyl; Introduction Continuous-flow processing is used in the chemical

Dipolar addition to cyclic vinyl sulfones leading to dual conformation tricycles

• Steven S. Y. Wong,
• Michael G. Brant,
• Christopher Barr,
• Allen G. Oliver and
• Jeremy E. Wulff

Beilstein J. Org. Chem. 2013, 9, 1419–1425, doi:10.3762/bjoc.9.159

• expedient regio- and stereospecific synthesis of five-membered ring N-, O- or S-containing heterocycles [4][5]. Various 1,3-dipoles can be used, including nitrones [6], azomethine ylides [7], diazoalkanes [8][9] and many others [10][11][12]. α,β-Unsaturated carbonyl compounds are often found to be good

New simple synthesis of ring-fused 4-alkyl-4H-3,1-benzothiazine-2-thiones: Direct formation from carbon disulfide and (E)-3-(2-aminoaryl)acrylates or (E)-3-(2-aminoaryl)acrylonitriles

• Qiuping Ding,
• Yuqing Lin,
• Guangni Ding,
• Fumin Liao,
• Xiaoyan Sang and
• Yi-Yuan Peng

Beilstein J. Org. Chem. 2013, 9, 460–466, doi:10.3762/bjoc.9.49

• or isothiocyanates bearing one o-substituted α,β-unsaturated carbonyl fragment promoted by the CS2/TBAF system [17]. However, both the low yields (30–60%) of the products and the substrate limitations outweigh their advantages. As part of a continuing effort in our laboratory toward the development

Reactions of salicylaldehyde and enolates or their equivalents: versatile synthetic routes to chromane derivatives

• Ishmael B. Masesane and
• Zelalem Yibralign Desta

Beilstein J. Org. Chem. 2012, 8, 2166–2175, doi:10.3762/bjoc.8.244

• (5), followed by an intramolecular aldol reaction and final dehydration to give the desired chromene derivative. Related work involving asymmetric reaction of salicylaldehyde derivatives and α,β-unsaturated carbonyl compounds in the synthesis of 2-phenylchromenes was reported by Li and co-workers

Synthesis and ring openings of cinnamate-derived N-unfunctionalised aziridines

• Alan Armstrong and
• Alexandra Ferguson

Beilstein J. Org. Chem. 2012, 8, 1747–1752, doi:10.3762/bjoc.8.199

• carbonyl compounds. Our method produces trans-NH-aziridines from α,β-unsaturated carbonyl compounds in good to excellent yield with high diastereoselectivity (Figure 1) [21]. An N–N ylide (aminimine) is the presumed active intermediate, formed from the reaction of a tertiary amine promoter and an aminating

• dihydroxylation, conversion to a cyclic sulfate, ring opening with azide, and finally ring closure to afford the NH-aziridine [18]. We recently reported [21][22] a nucleophilic aziridination methodology [23][24][25][26][27][28][29][30] that allows access to NH-aziridines in a single step from α,β-unsaturated

Construction of cyclic enones via gold-catalyzed oxygen transfer reactions

• Leping Liu,
• Bo Xu and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2011, 7, 606–614, doi:10.3762/bjoc.7.71

• - or Lewis acid-catalyzed oxygen transfer from carbonyl to carbon–carbon triple bond, the so-called alkyne–carbonyl metathesis, has attracted much attention because this atom economical transformation generates α,β-unsaturated carbonyl derivatives which are of great interest in synthetic organic

• ; gold-catalyzed; oxonium; oxygen transfer; Review α,β-Unsaturated carbonyl derivatives are not only important building blocks in synthetic organic chemistry, but are also a significant motif in natural products and biologically active compounds [1][2][3][4][5][6][7][8]. The construction of the

Michael-type addition of azoles of broad-scale acidity to methyl acrylate

• Sławomir Boncel,
• Kinga Saletra,
• Barbara Hefczyc and
• Krzysztof Z. Walczak

Beilstein J. Org. Chem. 2011, 7, 173–178, doi:10.3762/bjoc.7.24

• of various azoles to α,β-unsaturated carbonyl and nitro derivatives has been frequently exploited in the synthesis of precursors of biologically active compounds [3][7][8][9][10][11][12][13][14][15]. This reaction, although structurally restricted to α,β-unsaturated carbonyl compounds and their

Aroylketene dithioacetal chemistry: facile synthesis of 4-aroyl- 3-methylsulfanyl- 2-tosylpyrroles from aroylketene dithioacetals and TosMIC

• H. Surya Prakash Rao and
• S. Sivakumar

Beilstein J. Org. Chem. 2007, 3, No. 31, doi:10.1186/1860-5397-3-31

• to general α,β-unsaturated carbonyl compounds. Background The α-aroylketene dithioacetals (AKDTAs) 1 are useful three-carbon synthones extensively employed for the synthesis of a wide variety of heterocyclic compounds and also in several aromatic ring annulation reactions. [1][2] The AKDTAs are α,β

• -unsaturated carbonyl compounds with two electron-donating alkylsulafanyl groups on one end and an electron-withdrawing aroyl group at the other end of the double bond, i.e., they are "push-pull" alkenes. Depending on the nucleophile and the reaction conditions either 1,2- or 1,4-necleophilc additions on 1 are

Variations in product in reactions of naphthoquinone with primary amines

• Marjit W. Singh,
• Anirban Karmakar,
• Nilotpal Barooah and
• Jubaraj B. Baruah

Beilstein J. Org. Chem. 2007, 3, No. 10, doi:10.1186/1860-5397-3-10

• based on the established fact that the presence of a carbonyl group favors γ-attack on a α-β unsaturated carbonyl over an imine; we would like to put forward the first path. But it is still not clear about the aromatization process, whether it is a unimolecular, or a bimolecular process. Work is in

One-pot synthesis of novel 1H-pyrimido[4,5-c][1,2]diazepines and pyrazolo[3,4-d]pyrimidines

• Dipak Prajapati,
• Partha P. Baruah,
• Baikuntha J. Gogoi and
• Jagir S. Sandhu

Beilstein J. Org. Chem. 2006, 2, No. 5, doi:10.1186/1860-5397-2-5

• discussions The synthesis of pyrimido [4,5-c][1,2]diazepine-6,8-dione 3a was accomplished by reacting equimolar quantities of 1,3-dimethyl-6-hydrazino uracil 1 and α,β-unsaturated carbonyl compound 2a in ethanol under reflux for 3 h (monitored by TLC). The suspension of 6-hydrazino uracil 1 first disappeared

• through involvement of an azine (obtained from oxidation of hydrazine group). Similarly other α,β-unsaturated carbonyl compounds 2b-e were reacted and the corresponding pyrimido[1,2]diazepines 3b-e were obtained in 78–90% yields and were characterized fully by spectroscopic and elemental analyses. The IR