Substrate dependent reaction channels of the Wolff–Kishner reduction reaction: A theoretical study

• Shinichi Yamabe,
• Guixiang Zeng,
• Wei Guan and
• Shigeyoshi Sakaki

Beilstein J. Org. Chem. 2014, 10, 259–270, doi:10.3762/bjoc.10.21

• at the reaction center was prepared by the use of Z matrices. For instance, in the gas phase SN2 reaction Cl− + H3C–Br → Cl–CH3 + Br−, Cl···C and C···Br intermediate distances were assumed. The geometry was optimized under the constraint of the fixed Cl–C and C–Br distances. After the partial

Triol-promoted activation of C–F bonds: Amination of benzylic fluorides under highly concentrated conditions mediated by 1,1,1-tris(hydroxymethyl)propane

• Pier Alexandre Champagne,
• Alexandre Saint-Martin,
• Mélina Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2013, 9, 2451–2456, doi:10.3762/bjoc.9.283

• the reaction are currently underway in our laboratory. SN2 reaction of activated alkyl fluorides and calculated transition state for the reaction of morpholine with benzyl fluoride with three molecules of water. Proposed activation of C–F bonds mediated by a triol. Initial screening. Fine-tuning

One-pot sequential synthesis of isocyanates and urea derivatives via a microwave-assisted Staudinger–aza-Wittig reaction

• Diego Carnaroglio,
• Katia Martina,
• Giovanni Palmisano,
• Andrea Penoni,
• Claudia Domini and
• Giancarlo Cravotto

Beilstein J. Org. Chem. 2013, 9, 2378–2386, doi:10.3762/bjoc.9.274

• undesired side-product formation and, consequently, a lower yield. Therefore, the choice of the right solvent and reaction conditions is the key to the success of this transformation. Our initial attempts focused on the synthesis of azido derivatives in MeCN. Although generally performed in DMF, the SN2

• reaction of alkyl bromide with NaN3 can also be performed in MeCN. NaN3 is insoluble in MeCN at room temperature (<0.005 g/100 mL), but its solubility increases at higher temperatures. Furthermore, NaBr generated during the nucleophilic substitution is insoluble and can be removed by filtration as can the

Kinetics and mechanism of the anilinolysis of aryl phenyl isothiocyanophosphates in acetonitrile

• Hasi Rani Barai and
• Hai Whang Lee

Beilstein J. Org. Chem. 2013, 9, 615–620, doi:10.3762/bjoc.9.68

• congestion in the bond-making process in a stepwise process with a rate-limiting bond formation (or a normal SN2 reaction) [13][14][15]. The magnitudes of the kH/kD values invariably decrease as the aniline becomes less basic. The magnitudes of the kH/kD values invariably increase for X = (4-MeO, 4-Me, H, 4

The chemistry of bisallenes

• Henning Hopf and
• Georgios Markopoulos

Beilstein J. Org. Chem. 2012, 8, 1936–1998, doi:10.3762/bjoc.8.225

• coming close to a general route to introduce functionality into bisallenes at the present time seems to be the double SN2'-reaction of 2,4-hexadiyne-1,6-diol (63, e.g. R1 to R4 = aryl) and its derivatives with various nucleophiles (Scheme 13) [49][50]. Thus, heating the diols 63 with an aromatic or

Alkene selenenylation: A comprehensive analysis of relative reactivities, stereochemistry and asymmetric induction, and their comparisons with sulfenylation

• Vadim A. Soloshonok and
• Donna J. Nelson

Beilstein J. Org. Chem. 2011, 7, 744–758, doi:10.3762/bjoc.7.85

• ]. It is well established that the rate determining step in benzenesulfenyl chloride addition is the formation of thiiranium intermediate; specifically the alkene π electrons displace Cl− in an SN2 reaction to give the thiiranium ion [89]. On the other hand, recent studies ruled out the formation of the

Asymmetric synthesis of tertiary thiols and thioethers

• Jonathan Clayden and
• Paul MacLellan

Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68

• the preparation of certain families of tertiary thiols and thioethers. For example, SN2 displacement of a mesylate leaving group by thiophenol can be accomplished using α-hydroxy esters 2 (Scheme 1) [12]. The presence of the α-ester group of 3 promotes SN2 reaction in two ways: The electron

• cyanohydrins, can also be made to undergo SN2 reaction with sulfur nucleophiles [13]. However, substitution of the quaternary α-(sulfonyloxy)nitrile 11 is very slow, and conversion of 11 to 12 with potassium thioacetate in DMF proceeds in only 35% yield after 72 hours. SN2 displacement of the leaving group by

Oxidative cyclization of alkenols with Oxone using a miniflow reactor

• Yoichi M. A. Yamada,
• Kaoru Torii and
• Yasuhiro Uozumi

Beilstein J. Org. Chem. 2009, 5, No. 18, doi:10.3762/bjoc.5.18

• subsequent oxirane ring opening with the intramolecular oxygen nucleophile (an intramolecular SN2 reaction) to afford the product 2 stereospecifically [44][45]. It should be noted that the miniflow cyclization of 1a was continuously carried out to give a quantitative conversion of 2a over 2 h. Conclusion In

Efficient 1,4-addition of α-substituted fluoro(phenylsulfonyl)methane derivatives to α,β-unsaturated compounds

• G. K. Surya Prakash,
• Xiaoming Zhao,
• Sujith Chacko,
• Fang Wang,
• Habiba Vaghoo and
• George A. Olah

Beilstein J. Org. Chem. 2008, 4, No. 17, doi:10.3762/bjoc.4.17

• of PMe3 to alkene 4 generates the dipolar intermediate. The latter abstracts a proton from the α-fluoro-substituted methylene derivative 3, followed by an intermolecular SN2 reaction to furnish the desired product 5 and the release of PMe3 (Scheme 1). The mechanism supports the fact that the less