Stereoselective free radical phenylsulfenylation of a nonactivated delta-carbon atom
Stereoselektivno slobodnoradikalsko fenilsulfenilovanje neaktiviranog δ-ugljenikovog atoma
Апстракт
A stereoselective free radical introduction of a phenylthio group onto a nonactivated methyl group in the 8-position, adjacent to a prochiral carbon atom, was achieved by photolysis of (-)-menthyl benzenesulfenate in the presence of hexabutylditin and (1R, 3R, 4S, 8S)-9-phenylthiomenthot (4) was obtained with 91 % optical purity. High stereoselectivity of the reaction was calculated (ab initio MP2/6-3 1G**) to be the consequence of the difference in the transition state eneregies (DeltaDeltaG(#) = 5.08 kJ/mol) favouring 4 relative to (1R,3R,4S,8R)-9-phenylthiomenthoI (5). The absolute configuration of a the new chiral carbon atom was confirmed by its correlation with the corresponding menthane-3,9-diol of known stereochemistry.
Fotolizom (–)-mentil-benzensulfenata u prisustvu heksabutil-dikalaja izvršeno je stereoselektivno uvođenje feniltio grupe na neaktiviranu metil grupu u δ-položaju koja je susedna prohiralnom ugljenikovom atomu i dobiven je (1R 3R, 4S, 8S)-9-feniltio-mentol (4) sa 91 % optičke čistoće. Visoka stereoselektivnost reakcije, potvrđena računom (ab initio MP2/6-21G**) posledica je razlike u energijama prelaznih stanja ΔΔG# = 5.08 kJ/mol) koja favorizuje nastajanje 4 u odnosu na (1R, 3R, 4S, 8R)-9-feniltio-mentol (5). Apsolutna konfiguracija novog hiralnog ugljenikovog atoma potvrđena je korelacijom s odgovarajućim mentan-3,9-diolom poznate stereohemije.
Кључне речи:
radical reactions / stereoselective reactions / stereoselective reactions / C-H activation / C-H activation / absolute configurations / absolute configuration / ab initio calculations / ab initio calculations / menthyl benzenesulfenate / menthyl benzenesulfenate / 9-phenylthiomenthol / 9-phenylthiomentholИзвор:
Journal of the Serbian Chemical Society, 2004, 69, 10, 737-747Издавач:
- Serbian Chemical Soc, Belgrade
DOI: 10.2298/JSC0410737P
ISSN: 0352-5139
WoS: 000224923100002
Scopus: 2-s2.0-31544437728
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Petrović, G. AU - Saičić, Radomir AU - Došen-Mićović, Ljiljana AU - Čeković, Živorad PY - 2004 UR - https://cherry.chem.bg.ac.rs/handle/123456789/668 AB - A stereoselective free radical introduction of a phenylthio group onto a nonactivated methyl group in the 8-position, adjacent to a prochiral carbon atom, was achieved by photolysis of (-)-menthyl benzenesulfenate in the presence of hexabutylditin and (1R, 3R, 4S, 8S)-9-phenylthiomenthot (4) was obtained with 91 % optical purity. High stereoselectivity of the reaction was calculated (ab initio MP2/6-3 1G**) to be the consequence of the difference in the transition state eneregies (DeltaDeltaG(#) = 5.08 kJ/mol) favouring 4 relative to (1R,3R,4S,8R)-9-phenylthiomenthoI (5). The absolute configuration of a the new chiral carbon atom was confirmed by its correlation with the corresponding menthane-3,9-diol of known stereochemistry. AB - Fotolizom (–)-mentil-benzensulfenata u prisustvu heksabutil-dikalaja izvršeno je stereoselektivno uvođenje feniltio grupe na neaktiviranu metil grupu u δ-položaju koja je susedna prohiralnom ugljenikovom atomu i dobiven je (1R 3R, 4S, 8S)-9-feniltio-mentol (4) sa 91 % optičke čistoće. Visoka stereoselektivnost reakcije, potvrđena računom (ab initio MP2/6-21G**) posledica je razlike u energijama prelaznih stanja ΔΔG# = 5.08 kJ/mol) koja favorizuje nastajanje 4 u odnosu na (1R, 3R, 4S, 8R)-9-feniltio-mentol (5). Apsolutna konfiguracija novog hiralnog ugljenikovog atoma potvrđena je korelacijom s odgovarajućim mentan-3,9-diolom poznate stereohemije. PB - Serbian Chemical Soc, Belgrade T2 - Journal of the Serbian Chemical Society T1 - Stereoselective free radical phenylsulfenylation of a nonactivated delta-carbon atom T1 - Stereoselektivno slobodnoradikalsko fenilsulfenilovanje neaktiviranog δ-ugljenikovog atoma VL - 69 IS - 10 SP - 737 EP - 747 DO - 10.2298/JSC0410737P ER -
@article{ author = "Petrović, G. and Saičić, Radomir and Došen-Mićović, Ljiljana and Čeković, Živorad", year = "2004", abstract = "A stereoselective free radical introduction of a phenylthio group onto a nonactivated methyl group in the 8-position, adjacent to a prochiral carbon atom, was achieved by photolysis of (-)-menthyl benzenesulfenate in the presence of hexabutylditin and (1R, 3R, 4S, 8S)-9-phenylthiomenthot (4) was obtained with 91 % optical purity. High stereoselectivity of the reaction was calculated (ab initio MP2/6-3 1G**) to be the consequence of the difference in the transition state eneregies (DeltaDeltaG(#) = 5.08 kJ/mol) favouring 4 relative to (1R,3R,4S,8R)-9-phenylthiomenthoI (5). The absolute configuration of a the new chiral carbon atom was confirmed by its correlation with the corresponding menthane-3,9-diol of known stereochemistry., Fotolizom (–)-mentil-benzensulfenata u prisustvu heksabutil-dikalaja izvršeno je stereoselektivno uvođenje feniltio grupe na neaktiviranu metil grupu u δ-položaju koja je susedna prohiralnom ugljenikovom atomu i dobiven je (1R 3R, 4S, 8S)-9-feniltio-mentol (4) sa 91 % optičke čistoće. Visoka stereoselektivnost reakcije, potvrđena računom (ab initio MP2/6-21G**) posledica je razlike u energijama prelaznih stanja ΔΔG# = 5.08 kJ/mol) koja favorizuje nastajanje 4 u odnosu na (1R, 3R, 4S, 8R)-9-feniltio-mentol (5). Apsolutna konfiguracija novog hiralnog ugljenikovog atoma potvrđena je korelacijom s odgovarajućim mentan-3,9-diolom poznate stereohemije.", publisher = "Serbian Chemical Soc, Belgrade", journal = "Journal of the Serbian Chemical Society", title = "Stereoselective free radical phenylsulfenylation of a nonactivated delta-carbon atom, Stereoselektivno slobodnoradikalsko fenilsulfenilovanje neaktiviranog δ-ugljenikovog atoma", volume = "69", number = "10", pages = "737-747", doi = "10.2298/JSC0410737P" }
Petrović, G., Saičić, R., Došen-Mićović, L.,& Čeković, Ž.. (2004). Stereoselective free radical phenylsulfenylation of a nonactivated delta-carbon atom. in Journal of the Serbian Chemical Society Serbian Chemical Soc, Belgrade., 69(10), 737-747. https://doi.org/10.2298/JSC0410737P
Petrović G, Saičić R, Došen-Mićović L, Čeković Ž. Stereoselective free radical phenylsulfenylation of a nonactivated delta-carbon atom. in Journal of the Serbian Chemical Society. 2004;69(10):737-747. doi:10.2298/JSC0410737P .
Petrović, G., Saičić, Radomir, Došen-Mićović, Ljiljana, Čeković, Živorad, "Stereoselective free radical phenylsulfenylation of a nonactivated delta-carbon atom" in Journal of the Serbian Chemical Society, 69, no. 10 (2004):737-747, https://doi.org/10.2298/JSC0410737P . .