
konia-enee praticharya

sendriya rasayana saastramlo, konia-enee praticharya anedi eestar ledhaa keaton vanti anolable carbonyl mariyu alkine ledhaa alkeen madhya oka intramolecular cyclisation praticharya, idhi kotta carbon-carbon bandhamtho chakriya utpattini istundi. modata J nivedinchinatlugaa. emm. konia mariyu pii. percheck, konia-enee praticharya anedi enee praticharya yokka heteroautum analog, idhi enaalnu enee bhaagamgaa upayogistundi. itara pericyclic praticharyala maadirigaane, asalu konia-enee praticharyaku konasaagadaaniki adhika ushnogratalu avasaramayyayi, dheeni vistruta anuvartanaanni parimitam chesindi. ayithe, tadupari merugudalalu, mukhyamgaa loha utprerakam, pratispandana paridhini gananeeyamgaa vistarinchadaaniki daariteesaayi. tatphalitamgaa, sanklishta anuvulu mariyu sahaja utpattula samshlaeshanhaloo konia-enee praticharya yokka vividha roopaalu upayoginchabaddaayi.
charitra mariyu yantraangam.
1960la chivaralo, rasayana shaastravetta zeane-maerii konia prayogasaala chinna carbocyclic anuvulanu, mukhyamgaa carbonylsto eni-rakam praticharyala utpattulugaa parisoedhimchimdi. eee prayatnaalu 1975loe "asantrupta carbonyl sammelanaala ushna chakrakara" anae sheershikato sameeksha patramlo mugisai.anie.
daani asalu vyakteekaranalo, konia-enee praticharyalo ε, ζ-asantrupta keatonelu ledhaa aldehydela intramolecular cyclisation untundi, idhi teevramaina vaedi meeda kriyaatmaka cyclopentinelaku untundi. pratipaadita yantraangam aaru-sabhyula, enee praticharya vanti parivartana sthithini prerepinchindi, dheenilo enol toutomer lockettu alkeentho samishtiga pratispandistundi.
adhe paristhitulu tagina uparitalaalato aaru mariyu tommidi-sabhyula valayalanu istayani kanugonabadindi, ayithe takkuva digubadi mariyu diasteriocelectivitiviti. γ, δ-mariyu δ vishayamlo, ε-asantrupta keatonelu, samathoulyam cyclopropane ledhaa cyclobutane kante sarala utpattiki anukuulamgaa untundi. alkynyl keatonelu ushna paristhitulalo kooda chakrakaramga unnatlu kanugonabadindi, ivi samyoga mariyu daataveyabadina chakriya enonla misramaanni istayi.
rendu mukhya lopaalu prarambha konia-enee praticharyanu vistrutamgaa amalu cheyadaanni nirodhinchaayi. modata, adanapu kriyaatmaka samuuhaalatoe unna anuvulu tarachugaa maarpidiki avasaramaina adhika ushnogratalaku anukuulamgaa undavu. rendavadi, regio-mariyu diasterioselectivitiviti puurtigaa uparitalampai aadharapadi untundi, idhi utpatti yokka dhoranipai takkuva ledhaa etuvanti niyantrananu andistundi.
purogati.
konia-enee praticharyanu kanugonna dasaabdaala taruvaata, aneka merugudalalu telikapati praticharya paristhitulaku mariyu utpatti stereo-mariyu regiochemistrypy ekkuva niyantranaku anumatinchaayi. udaaharanaku, carbonyl bhaagam, gatamlo keaton ledhaa aldehyde, pratyaamnaaya β-ketoester ledhaa malonate esterga maarindi. ituvanti carbonyls marinta sulabhamgaa anolyse avtayi, kaavalasina enol toutomercu merugaina praapyatanu istayi. adanamgaa, alkeen bhaagam alkeentho bharti cheyabadindi, idhi baldwyn niyamaalaku anugunamgaa merugaina cyclisation ivvadame kakunda, marinta parivartanalaku upayogakaramaina handlega upayogapade alkeen kaligina utpattini kooda andinchindi. chivaraga, iteevali prayatnaalalo loha-madhyavartitva mariyu loha-utpreraka sankuvu-enee praticharyalu unnaayi, veetini kairal ligandlanu upayoginchi asamanamga maarchavacchu.
kriyaaseelata reetulu.
eee purogatulu operative activation mode dwara vargeekarinchabadina aidu pradhana rakaala konia-enee praticharyalanu utpatti cheshai avi, anolate, alkine ledhaa enee-yain activation mariyu okati ledhaa rendu-metal dual activation. konia-enee vaividhyaala yokka vidhanalu prarambha enee-vanti cyclisation nundi bhinnamgaa unnappatikee, avi ippatikee konia-enee ledhaa konia-enee-rakam praticharyalugaa pariganhinchabadutunnaayani gamaninchandi. adanamgaa, konni konia-enee praticharya vyavasthala sanklishtata kaaranamgaa, nijamaina yantraangam aneka vibhina kriyaaseelata reetula madhya ekkado undavacchu.
sakriyam cheyu anolate cheyandi.
anolate activation anedi saralamaina konia-enee activation mode. eee paddhatiloo, carbonyl prarambha padaartham enbuli, naa ledhaa tbook vanti balamaina punaaditoe chikitsa cheyabadutundi, idhi loha-sthireekarinchina anoletnu yerparustundi, idhi appudu kattabadina alkainpai daadi chesi loha kaatayaannu badilee chestundi. anolate kriyaaseelataku prarambha udaaharana 1999loe taguchi mariyu sahodyogulu nivedinchaaru. utpreraka punaadi samakshamlo, alkynyl-pratyaamnaaya malonate estarlu sambandhita cyclopentenlaku sulabhamaina cyclisationku lonavutayani rachayitalu kanugonnaru. pratyaamnaaya sinoacetate, sulphonylasetate mariyu phosphonoacetate analogsto kooda adhika digubadini pondaaru.
alkine kriyaaseelata.
alkin kriyaaseelata dwara konasagutunna konia-enee praticharyalalo, tagina chivari parivartana loham (AU, Ag, pt, pd) alkinku samanvayaparustundi mariyu daani electrophylicityni penchutundi; tadwara, carbonyl yokka enol toutomer marinta sulabhamgaa daadi cheyagaladu. toast mariyu itarulu. 2004loe alkine kriyaaseelataku modati udaaharanalalo rendu udaaharanalu. catanic ou (ii) complexenu upayoginchi, rachayitalu leanier β-keatoster prarambha padaarthaala nundi aneka rakaala cyclised utpattulanu roopondinchaaru. mukhyamgaa, praticharyalu telikapati paristhitulalo amalu cheyabadataayi mariyu adhika diasteriocelectivitivitine istayi. antekakunda, alkine tethernu moodu carbonla nundi renduku tagginchadam dwara, pratyaamnaaya cyclopentinelanu kooda access cheyavachu.
enee-yain kriyaaseelata.
aidu reetulalo athi takkuva saadhaaranamaina enee-yain kriyaaseelataloo, oke loha jaathi enal alkeen mariyu kattabadina alkeentho samanvayaparustundi, ekakaalamlo praticharya kosam rendu moitylanu sakriyam chestundi. nickel, cobalt mariyu renium complexelu annee eee paddhatiloo upayoginchabaddaayi. oka praatinidhya udaaharananu malacria mariyu itarulu nivedinchaaru. 1994loe, dheenilo pratyamnaayamgaa unna alkynyl β-ketoesterku cyclopentadianyl cobalt complexes mariyu vikiranam dwara chikitsa chesi, pratyamnaayamgaa unna methylene cyclopentennu andinchindi.
oka-loha dwandwa kriyaaseelata.
oke loham dwara dwandwa kriyaaseelatanu prabhaavitam cheyadaaniki, anoletnu sakriyam chese adhe loha jaatulu kooda aalkaintho sankarshana chendutaayi. khachitamaina yantraamgaalu sarigga ardham kaanappatikee, kesuku kesuku maarutuu unnappatikee, inn, jdn, phe mariyu kyuu vanti lohaalu eee mode dwara panicheyaalani pratipaadinchabaddaayi. oka-loha dwandwa kriyaaseelata dwara konasaagutundani bhaavinche oka praticharya vyavastha shaa mariyu itarulu abhivruddhi chesaaru. 2014loe utpreraka phe (III)-(salen) complexenu upayoginchi, shaa mariyu sahodyogulu alkynyl-kattabadina β-ketosterlu mariyu daani analogues shreni nundi kairal cyclopentenlanu access cheyagaligaaru. eee praticharya vistruta shreni keatonelanu (phenyl, homoallil, cyclopropyl, 2-furil modalainavi) thattukogaligindi.), estarlu (ethyl, tert-beautile modalainavi.), mariyu ester analogues (nitro, syano, sulphonyl modalainavi).).
rendu-loha dwandwa kriyaaseelata.
rendu-loha dwandwa kriyaaseelata anedi anolate kriyaaseelata mode mariyu alkin kriyaaseelata mode kalayikanu oke praticharya vyavasthagaa suuchistumdi. saadhaaranamgaa, oka gatti, oxophilic loham (k, Na, Ag) anolate oxygennu sakriyam chestundi, ayithe oka mruduvaina, carbophilic loham (pd, cu, mo) aalkaintho samanvayaparustundi. ayithe, konni sandarbhaallo, prati loham yokka khachitamaina paatra aspashtamgaa undhi. udaaharanaku, 2005 adhyayanam loe, itarulu. pd (ii) phosphine complexes mariyu yb (otf) thoo alkynyl-kattabadina β-ketoester chikitsa sambandhita cyclopentenku asamaana cyclisation prabhaavitam chesindani kanugonnaru. pidi-anolate vaibi-activated aalkainloki jodistundani pratipaadinchabadindi, ayithe alkinela pidi activationku kooda udaaharana undhi.
mottam samshlaeshanhaloo anuvartanaalu.
avi aaa-utprerakamaina konia-enee praticharyalanu abhivruddhi chesina taruvaata, toste mariyu sahodyogulu alcoloid sahaja utpatti lycopladine eah vaipu ituvanti parivartananu upayoginchaaru. kairal cyclohexenone 1 nundi praarambhinchi, enon functionalisationla shreni silil enal eethar 2 nuu konia-enee purvagaamigaa ichindi. cyclisation prabhaavitam cheyadaaniki, 2nii utpreraka acclel (pfhetch) mariyu agbfto chikitsa chesi vinail iodide 3nii adhika digubadilo oke diasteriomerga andinchindi. (+)-lycopladine eah nuu enimidi dasallo mariyu mottam digubadi 17 saatam ivvadaaniki anuvu yokka migilina bhaagam moodu dasallo puurtayimdi.
2012loe, karrira mariyu itarulu. samslaeshanha cheyabadina, erra algay laurencia majuskula nundi verucheyabadina hologenated terpene, mariyu chivari dasagaa yuu-utprerakamaina konia-enee cyclisation upayoginchindi. saikil 6 nundi 11 dasallo silil enol eethar 7 nuu pondina taruvaata, 4 mariyu enon 5 madhya dials-alder cycloload utpatti ayina rachayitalu 65 saatam digubadilo tricycle 8 nuu andinchadaaniki 7 nundi 50 moll% ekavaren utprerakaaniki lobadi untaaru. eee sammelanam appudu exo-methylene yokka chlorination dwara vivarinchabadutundi.
2020loe, yang mariyu sahodyogulu (+)-vaihonsin yokka asamaana samslaeshanha samayamlo diasterioselective konia-enee praticharyanu upayoginchaaru, idhi podocarpus totara varr nundi nirmanatmakamga dattamaina terpenoid, dheenini 2017loe lii group samslaeshanha chesindi. vinailagus ester 9 modata kairal konia-ene puurvagaami 10kii aaru dasallo panichesindi. taruvaata dii. emm. ess. oo. loe tbook thoo 10 chikitsa saikil 11kii 83 saatam digubadini oke diasteriomerga ichindi. eee sammelanaaniki 15 dasallo (+)-vihoncine cherukovadaniki enimidi adanapu parivartanalu mariyu mottam digubadi 4 saatam avasaram.

