Iindlela ezi-3 ezinomdla ezakhiwa ziingcali zekhemistri kulo nyaka
nguBethany Halford
Iienzymes eziguquliweyo zakha iibhondi zeBiaryl
Iskimu esibonisa i-enzyme-catalyzed biaryl coupling.
Iingcali zekhemistri zisebenzisa iimolekyuli ze-biaryl, ezibonisa amaqela e-aryl adityaniswe ngebhondi enye, njenge-chiral ligands, iibhloko zokwakha izixhobo, kunye namayeza. Kodwa ukwenza i-biaryl motif ngeempendulo ze-metal-catalyzed reactions, ezifana ne-Suzuki kunye ne-Negishi cross-couplings, ngokuqhelekileyo kufuna amanyathelo aliqela okwenziwa ukwenza amaqabane okudibanisa. Ngaphezu koko, ezi mpendulo ze-metal-catalyzed reactions ziyawa xa zenza ii-biaryls ezinkulu. Ziphefumlelwe ngamandla ee-enzyme okuguqula ii-reactions, iqela elikhokelwa yi-Alison RH Narayan yaseYunivesithi yaseMichigan lisebenzise i-directed evolution ukwenza i-cytochrome P450 enzyme eyakha i-biaryl molecule ngokusebenzisa i-oxidative coupling yeebhondi ze-carbon-hydrogen ezinuka kamnandi. I-enzyme idibanisa iimolekyuli ezinuka kamnandi ukuze zenze i-stereoisomer enye ejikeleze ibhondi enokujikeleza okuthintelweyo (kubonisiwe). Abaphandi bacinga ukuba le ndlela yokwenza izinto eziphilayo inokuba lutshintsho olufana nesonka nebhotolo ekwenzeni iibhondi ze-biaryl (Nature 2022, DOI: 10.1038/s41586-021-04365-7).
IRESIPHI YEE-AMIN EZIPHEZULU EZITHEMBEKILEYO KWITYUWA ENCINZI
Iskimu sibonisa impendulo eyenza ii-amines zesithathu ukusuka kwezona zesibini.
Ukuxuba ii-catalysts zesinyithi ezilambileyo ngee-electron kunye nee-amines ezityebileyo ngee-electron kudla ngokubulala ii-catalysts, ngoko ke ii-reagents zesinyithi azinakusetyenziselwa ukwakha ii-amines ze-tertiary ezivela kwii-amines ze-secondary. UM. Christina White kunye noogxa bakhe kwiYunivesithi yase-Illinois Urbana-Champaign baqonda ukuba banokuyiphepha le ngxaki ukuba bongeza izinongo ezinetyuwa kwiresiphi yabo ye-reactant. Ngokuguqula ii-amines ze-secondary zibe zii-ammonium salts, ii-chemist zifumanise ukuba zinokuphendula ezi compounds nge-terminal olefins, i-oxidant, kunye ne-palladium sulfoxide catalyst ukwenza ii-amines ze-tertiary ezininzi ezinamaqela ahlukeneyo asebenzayo (umzekelo ubonisiwe). Ii-chemist zisebenzise le reaction ukwenza amayeza e-antipsychotic i-Abilify kunye ne-Semap kunye nokuguqula amayeza akhoyo angama-secondary amines, njenge-antidepressant Prozac, abe ngama-tertiary amines, bebonisa indlela ii-chemist ezinokwenza ngayo amayeza amatsha ngala akhoyo (Science 2022, DOI: 10.1126/science.abn8382).
I-AZAARENES AYISEBENZISI IKHABONI
I-Scheme ibonisa i-quinoline N-oxide eguqulwe yaba yi-N-acylindole.
Kulo nyaka iingcali zekhemistri zongeze kwi-repertoire yokuhlela iimolekyuli, eziziimpendulo ezenza utshintsho kwii-cores zeemolekyuli ezintsonkothileyo. Kumzekelo omnye, abaphandi baphuhlise utshintsho olusebenzisa ukukhanya kunye ne-asidi ukunqumla ikhabhoni enye kwi-azaarenes ezinamalungu amathandathu kwi-quinoline N-oxides ukuze kwenziwe i-N-acylíndoles enezangqa ezinamalungu amahlanu (umzekelo ubonisiwe). Le mpendulo, eyenziwe ziingcali zekhemistri kwiqela likaMark D. Levin kwiYunivesithi yaseChicago, isekelwe kwimpendulo ebandakanya isibane se-mercury, esikhupha amaza amaninzi okukhanya. ULevin kunye noogxa bakhe bafumanise ukuba ukusebenzisa i-diode ekhupha ukukhanya ekhupha ukukhanya kwi-390 nm kwabanika ulawulo olungcono kwaye kwabavumela ukuba benze i-reaction ngokubanzi kwi-quinoline N-oxides. Le mpendulo intsha inika abenzi beemolekyuli indlela yokuhlaziya ii-cores zeekhompawundi ezintsonkothileyo kwaye inokunceda iingcali zekhemistri zamayeza ezifuna ukwandisa iilayibrari zazo zamayeza afanelekileyo (Science 2022, DOI: 10.1126/science.abo4282).
Ixesha lokuthumela: Disemba-19-2022