Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

• Jón Atiba Buldt,
• Wang-Yeuk Kong,
• Yannick Kraemer,
• Masiel M. Belsuzarri,
• Ansh Hiten Patel,
• James C. Fettinger,
• Dean J. Tantillo and
• Cody Ross Pitts

Beilstein J. Org. Chem. 2024, 20, 3134–3143, doi:10.3762/bjoc.20.259

• -containing [2]staffane in the solid state. Keywords: pentafluorosulfanylation; [1.1.1]propellane; radical chain oligomerization; staffanes; strain-release; Introduction In various radical additions of X–Y across [1.1.1]propellane (1), functionalized oligomers known as [n]staffanes – with n > 1, where n

• synthetic challenge. Herein, we report proof-of-concept that our previous work on strain-release pentafluorosulfanylation of 1 [36] using SF5Cl (prepared in house [37] under mild oxidative fluorination conditions [38][39][40][41][42][43][44]) can be extended to the selective synthesis of the associated

• cooling; this highlights that the [2]staffanes synthesized during this study are also interesting from a fundamental structural standpoint. Results and Discussion Over the past few years, our group has begun to establish strain-release pentafluorosulfanylation as a viable strategy for C(sp3)–SF5 bond

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Controlled decomposition of SF₆ by electrochemical reduction

• Sébastien Bouvet,
• Bruce Pégot,
• Stéphane Sengmany,
• Erwan Le Gall,
• Eric Léonel,
• Anne-Marie Goncalves and
• Emmanuel Magnier

Beilstein J. Org. Chem. 2020, 16, 2948–2953, doi:10.3762/bjoc.16.244

• degradation of SF6 [17][18]. Other elegant approaches have described the use of SF6 as precursor of reagent for fluorination or pentafluorosulfanylation. Very interestingly, the photochemical activation of this gas was described and allowed the in situ transformation of alcohols into alkyl fluorides [19][20

N-Arylphenothiazines as strong donors for photoredox catalysis – pushing the frontiers of nucleophilic addition of alcohols to alkenes

• Fabienne Speck,
• David Rombach and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2019, 15, 52–59, doi:10.3762/bjoc.15.5

• well as the first pentafluorosulfanylation method starting from sulfur hexafluoride [2]. We are convinced that the value of phenothiazine derivatives in photoredox catalysis is still underestimated. While these compounds found widespread use in ATRA (atom transfer radical addition) polymerization [15

• ion. This was one of the features to use N-phenylphenothiazine for the photoactivation of SF6 for the pentafluorosulfanylation of styrenes [2]. This two photon concept can further be extended to the photoredox catalytically generation of hydrated electrons as very powerful reductants (E = −2.8 V (vs