CATALYST/METAL FREE REGIOSELECTIVE HYDROTHIOLATION OF TERMINAL ALLENES WITH IN SITU PREPARED DITHIOCARBAMIC ACIDS

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Ziyaei Halimehjani A., Nazari A., Dağalan Z., Nişancı B.

The 6th Organic Chemistry Congress with International Participation (OrgChemTr-6), Eskişehir, Türkiye, 10 Eylül 2025, ss.214, (Özet Bildiri)

  • Yayın Türü: Bildiri / Özet Bildiri
  • Basıldığı Şehir: Eskişehir
  • Basıldığı Ülke: Türkiye
  • Sayfa Sayıları: ss.214
  • Açık Arşiv Koleksiyonu: AVESİS Açık Erişim Koleksiyonu
  • Atatürk Üniversitesi Adresli: Evet

Özet

ABSTRACT


Hydrothiolation of carbon-carbon double bond, known as thiol-ene click reaction, is an important atom-economical stra-

tegy for the synthesis of organosulfur compounds with widespread applications in natural compounds, pharmaceuticals,


polymers, functional materials, and as synthetic intermediates. Although anti-Markovnikov addition of thiols to alkenes

is very well investigated over the last century, mainly via a radical-type mechanism, but regioelective hydrothiolation of

allenes is far less investigated and still remain a big challenge for scientists.1


Catalyst-free and regioselective anti-Marko-

vnikov hydrothiolation of allenes with in situ prepared dithiocarbamic acids is developed to afford the corresponding allyl


dithiocarbamates with 100% atom economy. This protocol has been successfully applied to various allene amides with dif-

ferent substitution patterns on the amine and tosyl groups. In addition, various primary and secondary amines were applied


successfully in this protocol to afford the target linear allyl dithiocarbamates in excellent yields. No branched product was

observed in this protocol. This three-component thiol-ene reaction can be considered as a new family of click reactions for

bioorthogonal invsetigations.2


Ts

N

R


CS2 NHR1R2 EtOH, rt, 5h

Ts

N

R

S N

S

R2

R1


+ +


Ts

N

R

S

N

S

R1 R2

not observed


Figure 1. Reaction scheme for the hydrothiolation of allenes.


Keywords: allenes , anti-Markovnikov hydrothiolation, catalyst-free

REFERENCES

[1] A. Ziyaei Halimehjani, Z. Dagalan, Z. Marjani, F. Gunduz, A. Dastan, and B. Nişancı, (2024). Catalyst/Metal/Solvent-Free

Markovnikov Hydrothiolation of Unactivated Alkenes with Dithiocarbamic Acids. The Journal of Organic Chemistry, 89(8), 5353-

5362. doi.org/10.1021/acs.joc.3c02722.

[2] A. Ziyaei Halimehjani, A. Nazari, Z. Dagalan, B. Nişancı, unpublished results.