Syn-selective silicon Mukaiyama-type aldol reactions of (pentafluoro-λ⁶-sulfanyl)acetic acid esters with aldehydes

• Anna-Lena Dreier,
• Andrej V. Matsnev,
• Joseph S. Thrasher and
• Günter Haufe

Beilstein J. Org. Chem. 2018, 14, 373–380, doi:10.3762/bjoc.14.25

• : aldol reaction; ester enolate; fluorine; SF5 compounds; stereochemistry; Introduction The classical acid- or base-catalyzed directed cross aldol reaction of an aldehyde and an enolizable second carbonyl compound is one of the most powerful and reliable carbon–carbon bond-forming transformations in

• aromatic [14][15] and heteroaromatic [16][17] SF5 compounds have become readily available and many applications have been described [18][19], the chemistry of aliphatic analogs is still underdeveloped [20]. Generally, the incorporation of SF5 groups into aliphatic positions is based on radical addition of

• [22]. There are not many transformations of aliphatic SF5 compounds described in the literature. Among them are the preparation and derivatization of SF5-aldehydes [23], Diels–Alder reactions [24][25][26], the “click reaction” of SF5-acetylenes with azides to form triazoles [27], and 1,3-dipolar

Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene

• Javier Ajenjo,
• Martin Greenhall,
• Camillo Zarantonello and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 192–197, doi:10.3762/bjoc.12.21

• than the trifluoromethyl group. Currently, the limiting factor for a more widespread use of SF5 compounds is the low accessibility of basic building blocks and the lack of understanding their chemical behavior. For aromatic SF5 compounds, two main synthetic approaches exist. The first one is a direct

Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

• Norbert Vida,
• Jiří Václavík and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 110–116, doi:10.3762/bjoc.12.12

• mechanism for the formation of the aliphatic SF5 compounds was presented and their chemical reactivity was investigated. SF5-substituted para-benzoquinone was synthesized; its oxidation led to an improved yield of 2-(pentafluorosulfanyl)maleic acid. The reaction of SF5-substituted maleic anhydride and para

• -withdrawing character [8] – similar to but more extreme than the trifluoromethyl group – makes SF5 compounds promising candidates for agrochemicals and pharmaceuticals [9]. Recent studies showed several cases where SF5 analogues of established compounds showed improved potency [10][11][12]. Limiting factors

• for a more widespread use of SF5 compounds are low accessibility of basic building blocks and the lack of understanding of their chemical behavior. Lack of availability of SF5 compounds is particularly evident in aliphatics where radical addition of expensive and toxic SF5Cl to unsaturated compounds

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• benzenethiols [10][11][12], or by the reaction of nitrophenyl disulfides with elemental fluorine [13][14][15][16]. Aromatic and heteroaromatic SF5 compounds are mostly prepared by the derivatization of commercial nitro-(pentafluorosulfanyl)benzenes [14][17][18][19][20][21][22][23][24][25][26][27] and approaches

• from SF5-aliphatics have also been studied [28][29][30]. The unique combination of properties the SF5 group imparts includes high chemical, thermal, and metabolic stability, strong electron-acceptor property, and high lipophilicity. Furthermore, applications of SF5 compounds in catalysis [31][32], life

Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry

• Teruo Umemoto,
• Lloyd M. Garrick and
• Norimichi Saito

Beilstein J. Org. Chem. 2012, 8, 461–471, doi:10.3762/bjoc.8.53

• , SF5 has high hydrolytic stability, which equals or exceeds CF3 [2]. These extraordinary properties render SF5 compounds highly attractive particularly in medicinal [5][6][7][8][9][10][11][12][13][14], agrochemical [15][16][17][18], and new material [19][20][21][22][23] chemistry and industry. However