Izindlela ezintathu ezijabulisayo ezakhiwa osokhemisi kulo nyaka
nguBethany Halford
Ama-enzyme aguqukile akhiwe ngamabhondi e-biaryl
Iskimu esibonisa ukuhlanganiswa kwe-biaryl okubangelwa yi-enzyme.
Osokhemisi basebenzisa ama-molecule e-biaryl, aqukethe amaqembu e-aryl ahlanganiswe ngesibopho esisodwa, njenge-chiral ligands, amabhlogo okwakha izinto, kanye nemithi. Kodwa ukwenza i-biaryl motif nge-reactions e-catalyzed metal, njenge-Suzuki ne-Negishi cross-couplings, ngokuvamile kudinga izinyathelo eziningana zokwenziwa ukuze kwenziwe abalingani bokuhlanganisa. Ngaphezu kwalokho, lokhu kusabela oku-catalyzed metal kuyawa lapho kwenziwa ama-biaryl amakhulu. Liphefumulelwe ikhono lama-enzyme lokuvuselela ukusabela, ithimba eliholwa yi-Alison RH Narayan wase-University of Michigan lisebenzise ukuvela okuqondisiwe ukudala i-enzyme ye-cytochrome P450 eyakha i-molecule ye-biaryl ngokuhlanganiswa kwe-oxidative kwezibopho ze-carbon-hydrogen ezi-aromatic. I-enzyme ihlanganisa ama-molecule aromatic ukuze idale i-stereoisomer eyodwa ezungeze isibopho esinokujikeleza okuvinjelwe (okuboniswe). Abacwaningi bacabanga ukuthi le ndlela ye-biocatalytic ingaba ushintsho lwesinkwa nebhotela lokwenza izibopho ze-biaryl (Nature 2022, DOI: 10.1038/s41586-021-04365-7).
IRESIPHI YAMA-AMIN ASE-TERTIARY ATHEMBEKILE KUSAWOTI OMNCANE
I-Scheme ikhombisa ukusabela okwenza ama-amine e-tertiary kusuka kwawesibili.
Ukuxuba ama-catalyst ensimbi alambile ngama-electron nama-amine acebile ngama-electron ngokuvamile kubulala ama-catalyst, ngakho-ke ama-reagent ensimbi awakwazi ukusetshenziselwa ukwakha ama-amine asezingeni eliphezulu avela kuma-amine asezingeni eliphezulu. UM. Christina White kanye nozakwabo e-University of Illinois Urbana-Champaign baqaphela ukuthi bangakwazi ukugwema le nkinga uma bengeza izinongo ezinosawoti eresiphi yabo ye-reactant. Ngokuguqula ama-amine asezingeni eliphezulu abe usawoti we-ammonium, osokhemisi bathole ukuthi bangasabela lawa ma-compounds ngama-olefin asezingeni eliphezulu, i-oxidant, kanye ne-palladium sulfoxide catalyst ukudala ama-amine amaningi asezingeni eliphezulu anamaqembu ahlukahlukene asebenzayo (isibonelo esibonisiwe). Osokhemisi basebenzise ukusabela ukwenza izidakamizwa ze-antipsychotic i-Abilify kanye ne-Semap kanye nokuguqula izidakamizwa ezikhona ezingama-amine asezingeni eliphezulu, njenge-antidepressant Prozac, zibe ama-amine asezingeni eliphezulu, bebonisa indlela osokhemisi abangenza ngayo izidakamizwa ezintsha ngalezo ezikhona (Science 2022, DOI: 10.1126/science.abn8382).
Ama-Azaarenes athola ukuncishiswa kwekhabhoni
I-Scheme ikhombisa i-quinoline N-oxide eguqulwe yaba yi-N-acylindole.
Kulo nyaka osokhemisi bangeze ohlwini lokuhlela ama-molecule, okuyizindlela ezenza izinguquko kuma-cores ama-molecule ayinkimbinkimbi. Esibonelweni esisodwa, abacwaningi bathuthukise ushintsho olusebenzisa ukukhanya ne-asidi ukusika ikhabhoni eyodwa kuma-azaarenes ayisithupha kuma-quinoline N-oxides ukuze kwakhiwe ama-N-acylíndoles anezindandatho ezinama-five-members (isibonelo esibonisiwe). Ukusabela, okwathuthukiswa osokhemisi eqenjini likaMark D. Levin eNyuvesi yaseChicago, kusekelwe ekusabeleni okwakuhilela isibani se-mercury, esasikhipha amaza amaningi okukhanya. ULevin nozakwabo bathole ukuthi ukusebenzisa i-diode ekhipha ukukhanya ekhipha ukukhanya ku-390 nm kwabanika ukulawula okungcono futhi kwabavumela ukuthi benze ukusabela kube okuvamile kwama-quinoline N-oxides. Ukusabela okusha kunikeza abenzi bama-molecule indlela yokulungisa kabusha ama-cores ama-compounds ayinkimbinkimbi futhi kungasiza osokhemisi bezokwelapha abafuna ukwandisa imitapo yabo yezidakamizwa (Science 2022, DOI: 10.1126/science.abo4282).
Isikhathi sokuthunyelwe: Disemba 19-2022