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

• -chloroalkyl aryl sulfides and selenides, respectively. Conversely, differences between the two reactions have been reported, but the sources of these differences have not been fully explained: While arenesulfenyl chlorides add to alkenes with an anti-Markovnikov orientation, areneselenenyl chlorides add with

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

• , sulfimines and sulfilimines [9]. Chiral sulfoxides and sulfonium ylids have themselves been extensively used as tools for asymmetric synthesis [3]. With regard to chiral sulfur(II) compounds – namely thiols and thioethers (sulfides) with chirality at carbon – methods available for their asymmetric

The allylic chalcogen effect in olefin metathesis

• Yuya A. Lin and
• Benjamin G. Davis

Beilstein J. Org. Chem. 2010, 6, 1219–1228, doi:10.3762/bjoc.6.140

• hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first

• . Keywords: allyl substituent effect; allyl sulfides; aqueous chemistry; olefin metathesis; protein modifications; Review Olefin metathesis is one of the most useful chemical transformations for forming carbon–carbon bonds in organic synthesis (Scheme 1) [1][2][3][4]. The broad utility of olefin metathesis

• substrates [27][28]. The effect of other allylic chalcogens in olefin metathesis Allyl sulfides are privileged substrates in olefin metathesis While there are many examples of allylic alcohols and ethers in metathesis, examples with allyl sulfide substrates were until recently noticeably few. This is

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

• Vladimir N. Boiko

Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88

• Vladimir N. Boiko Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya St. 5, 02094 Kiev, Ukraine 10.3762/bjoc.6.88 Abstract This review covers all of the common methods for the syntheses of aromatic and heterocyclic perfluoroalkyl sulfides, a class of compounds

• -process; perfluoroalkylation; perfluoroalkyl sulfides; SRF-introduction; Review 1. Introduction Perfluoroalkyl sulfides of aromatic and heterocyclic compounds have been an important aspect in the general development of organofluorine chemistry over the last twenty years. Alkyl aryl sulfides containing

• partly fluorinated aliphatic moieties have been widely used for a number of years. Their methods of preparation, for example, by the reaction of thiols with fluoro-olefins or with chloropolyfluoroalkanes are well known and have been widely used. In contrast, sulfides with fully fluorinated aliphatic

CAAC Boranes. Synthesis and characterization of cyclic (alkyl) (amino) carbene borane complexes from BF₃ and BH₃

• Julien Monot,
• Louis Fensterbank,
• Max Malacria,
• Emmanuel Lacôte,
• Steven J. Geib and
• Dennis P. Curran

Beilstein J. Org. Chem. 2010, 6, 709–712, doi:10.3762/bjoc.6.82

• , sulfides, etc.), NHC–borane complexes are highly stable in diverse environments. Complexes such as those shown in Figure 1 are white solids that can often be chromatographed if desired. Many such complexes resist decomplexation, oxidation, and both acidic and basic hydrolysis. Such NHC–boranes are

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

• Norio Shibata,
• Andrej Matsnev and
• Dominique Cahard

Beilstein J. Org. Chem. 2010, 6, No. 65, doi:10.3762/bjoc.6.65

• . (trifluoromethyl)dibenzoheterocyclic salts with electron-donating and electron-withdrawing substituents in benzene rings for fine tuning of their electrophilicity [12][13][14]. (Trifluoromethyl)dibenzothio- and selenophenium salts 5 and 6, respectively, were synthesized either by oxidation of the starting sulfides

The development and evaluation of a continuous flow process for the lipase- mediated oxidation of alkenes

• Charlotte Wiles,
• Marcus J. Hammond and
• Paul Watts

Beilstein J. Org. Chem. 2009, 5, No. 27, doi:10.3762/bjoc.5.27

• found widespread application in the conversion of nitriles to amides [32], aldehydes to acids [33], and sulfides to sulfones [34]. To enable comparison of the method developed here with batch investigations previously conducted, the oxidation of 1-methylcyclohexene (6) to 1-methylcyclohexene oxide (7

Enantiospecific synthesis of [2.2]paracyclophane- 4-thiol and derivatives

• Gareth J. Rowlands and
• Richard J. Seacome

Beilstein J. Org. Chem. 2009, 5, No. 9, doi:10.3762/bjoc.5.9

• ]paracyclophane compounds; aryl sulfonylation and the related sulfenylation facilitates the synthesis of sulfonic acids, sulfonamides and protected thiols [24][25][26] whilst directed metallation has allowed the formation of various sulfides [27][28][29][30]. Very few methodologies allow the synthesis of simple

• of enantiomerically pure 4-hydroxy[2.2]paracyclophane or application of our own sulfoxide-metal exchange protocol [31] would permit enantiospecific variants of either route, but neither has been reported. An elegant entry to a variety of racemic alkyl sulfides and sulfoxides by an SEAr reaction

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

• course. Reaction mechanism for phosphine catalyzed 1,4-addition to α,β-unsaturated compounds. Oxidation of sulfides and monofluorination of sulfones. PMe3-catalyzed reaction of fluoro(phenylsulfonyl)-substituted methane derivatives with methyl vinyl ketone and ethyl acrylate. K2CO3/DMF catalyzed 1,4

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

• 3f was isolated in only moderate yield (50%), together with unreacted sulfonimidoyl chloride 2a (28%), even after prolonged reaction times (24 h). The weakly basic cyanogen amine (pKa ~ 17), which had previously been used in the formation of N-cyano sulfilimines from sulfides using NBS as