konia-aine pratikriya

carbonic rasayan vigyaan mein, konia-aine pratikriya ack ester yaa keaton jaise ack anolysable carbonyl aur ack alkine yaa alkien key beach ack intramolicular cyclisation pratikriya haye, joe ack nae carbon-carbon bandhan key saath ack chakreeya utpaad detee haye. jaisa kii shuru mein jey dwara bataaya gayaa thaa. aim. konia aur pee. leey parchek, konia-aine pratikriya aine pratikriya kaa ack visham-pratiroop haye joe aine ghatak key roop mein ack anol kaa upayog kartaa haye. anya pericyclic pratikriyaon kii tarah, mool konia-aine pratikriya koo aage badhane key liye uchch tapman kii aavashyakta hoti haye, jisase iska vyaapak anuprayog seemit hoe jaataa haye. haalaanki, baad key sudhaaron, vishesh roop seey dhaatu utpreran mein, pratikriya key dayare kaa mahatvapurna vistaar huaa haye. natijatan, jatil anuon aur praakritik utpaadon key sanshleshan mein konia-aine pratikriya key vibhinn roopon kaa upayog kiya gayaa haye.
itihas aur tantra.
1960 key dashak key anta mein, rasaayanagya jeane-mairi konia kii prayogshala ney chhote carbocyclic anuon kii jaanch kii, vishesh roop seey carbonyl key saath aine-prakaar kii pratikriyaon key utpaadon key roop mein. inn prayason kii parinati 1975 key ack sameeksha patra mein hui jiska sheershak thaa "asantript carbonyl yaugikon kaa taapiya chakran."
apani mool abhivyakti mein, konia-aine pratikriya mein teevra taap parr karyatmak cyclopentance key liye ε, ζ-asantript keaton yaa aldehyde kaa intramolicular cyclisation shamil thaa. prastaavit tantra ney chhah-sadasyiya, aine pratikriya jaisi sankraman sthiti kaa ahwan kiya jisamen anole toutomer latkan alkien key saath thhos pratikriya kartaa haye.
samaan sthitiyaan upayukt substrate key saath chhah aur nau-sadasyiya valay dene key liye paaee gaeen, halanki cumm paidawar aur diasteriocelectivite key saath. γ, δ-aur δ key mamle mein, ε-asantript keaton, santulan cyclopropen yaa cyclobutane parr raikhik utpaad kaa paksh letaa haye. alkynil keaton bhee taapiya sthitiyon mein chakrakar paae gaye, joe sanyugmit aur chhod diye gaye chakreeya anones kaa mishran dete hain.
dou pramukh kamiyon ney praarambhik konia-aine pratikriya key vyaapak karyanvayan koo roque diyaa. sabse pahale, atirikt karyatmak samoohon vaale anu aksar roopaantaran key liye aavashyak uchch tapman key saath asangat they. doosara, regio-aur diasteriocelectivite poori tarah seey substrate parr nirbhar karati haye, joe utpaad key abhivinyas parr bahut cumm yaa koee niyantran naheen detee haye.
pragati.
konia-aine pratikriya kii khoj key baad key dashakon mein, kaee sudhaaron ney halki pratikriya sthitiyon aur utpaad stereo-aur regiochemistry key adhik niyantran kii anumati dee. udaaharan key liye, carbonyl ghatak, joe pahale ack keaton yaa aldehyde thaa, ack pratisthaapit β-ketoester yaa malonet ester bunn gayaa. iss tarah key carbonyl adhik aasaani seey anolyse hoe jaate hain, jisase vaanchhit anole toutomer taka behtar pahunch hoti haye. isake alawa, alkien ghatak koo ack alkine seey badal diyaa gayaa thaa, jisane naa kewal baldwyn key niyamon key anusaar behtar cyclisation diyaa, balki ack alkien yukt utpaad bhee prastut kiya joe aage key parivartanon key liye ack upayogi handle key roop mein kaary kartaa thaa. anta mein, haal key prayason mein dhaatu-madhyasth aur dhaatu-utprerit konia-aine pratikriyaaen shamil hain jinhen kieral ligand kaa upayog karke asmamit kiya jaa sakata haye.
sakriyan mode.
inn pragati ney paanch mukhya prakaar kii konia-aine pratikriyaon kaa utpaadan kiya haye joe operative sakriyan mode dwara visheshta haih arthaat, annolet, alkine, yaa aine-aine sakriyan, aur ack yaa dou-dhaatu dohri sakriyan. dhyaan dein kii halanki konia-aine prakaron key tantra praarambhik aine-jaise cyclisation seey alag hotey hain, phir bhee unhein konia-aine yaa konia-aine-prakaar kii pratikriya maanaa jaataa haye. isake alawa, kuchh konia-aine pratikriya pranaliyon kii jatilata key kaaran, sahee tantra kaee alag-alag sakriyan mode key beach kaheen hoe sakata haye.
sakriyan koo uttejit karein.
annolet sakriyan sabse saral konia-aine sakriyan mode haye. iss mode mein, carbonyl praarambhik samagri koo ack majboot aadhar key saath upchaarit kiya jaataa haye, jaise kii enbuli, naah, yaa tbook, ack dhaatu-sthir annolet banaane key liye, joe phir bandhe hue alkine parr hamla kartaa haye aur dhaatu key catayan koo sthanantarit kartaa haye. annolet sakriyan kaa ack praarambhik udaaharan 1999 mein taguchi aur sahakarmiyon dwara bataaya gayaa thaa. lekhakon ney paaya kii utprerak aadhar kii upasthiti mein, alkynil-pratisthaapit malonet ester sambandhit cyclopentance key liye saral cyclisation seey gujarate hain. pratisthaapit sinoasetate, sulphonylesatet aur phosphonestate analogue key saath uchch upaj bhee praapt kii gaee thee.
alkine sakriyan.
alkine sakriyan key madhyam seey aage badhane vaali konia-aine pratikriyaon mein, ack upayukt dair seey sankraman dhaatu (aeu, aejee, peaty, peedi) alkine key liye nirdeshank karati haye aur isaki electrophilicity koo badhaati haye; iss prakaar, carbonyl kaa anole tatomer adhik aasaani seey hamla curr sakata haye. toste aur anya. 2004 mein alkine sakriyan key pahale udaharanon mein seey dou kaa netritva kiya. ack cashionic aeu (aaee) parisar kaa upayog karke, lekhakon ney raikhik beeta-ketoester praarambhik samagri seey vibhinn prakaar key chakreeya utpaadon kaa gathan kiya. vishesh roop seey, pratikriyaaen halki sthitiyon mein sanchaalit hoti hain aur uchch diasteriocelectivite detee hain. isake alawa, alkine tither koo teen carbon seey dou carbon mein chhota karke, pratisthaapit cyclopentine taka bhee pahuncha jaa sakata haye.
aine-yine sakriyan.
aine-yine sakriyan mein, paanch tarikon mein seey sabse cumm samanya, ack ekal dhaatu prajaati anole alkien aur tatered alkine key saath samanvaya karati haye, joe ack saath pratikriya key liye donon moities koo sakriya karati haye. nickle, cobalt aur ranium parisaron koo iss tarah seey niyojit kiya gayaa haye. ack pratinidhi udaaharan malakriya aur anya dwara bataaya gayaa thaa. 1994 mein, jisamen ack alkynil pratisthaapit β-ketoester koo cyclopentadianil cobalt complexes aur vikiran key saath upchaarit kiya gayaa thaa taaki vighatit methylene cyclopenton diyaa jaa sakey.
ack-dhaatu dohri sakriyata.
ekal dhaatu dwara dohri sakriyata koo prabhaavit karane key liye, vahee dhaatu prajaati joe annolet koo sakriya karati haye, alkine key saath bhee baatchit karati haye. halanki sateek tantra koo bahut cumm samajha jaataa haye aur mamle seey mamle mein alag-alag honey kii sambhavana haye, dhatuon jaise kii inn, jdn, phee aur kyu koo iss mode key madhyam seey sanchaalit karane kaa prastaav haye. ack-dhaatu dohri sakriyata key madhyam seey aage badhane key liye socha gayaa ack pratikriya pranali shau aur anya dwara vikasit kiya gayaa haye. 2014 mein. ack utprerak phee (iii)-(selen) parisar kaa upayog karate hue, shau aur sahakarmi alkynile-sethard β-keatoster aur usake anuroopon kii ack shrinkhala seey kieral cyclopentance taka pahunchane mein saksham they. pratikriya ney keaton (phenyl, homolil, cyclopropyl, 2-furil, aadi) kii ack vistrit shrinkhala koo sahan kiya.), ester (ethyl, turt-butyle, aadi.), aur ester analogue (nitro, saino, sulphonyl, aadi.).
dou-dhaatu dohri sakriyata.
dou-dhaatu dohri sakriyan ack ekal pratikriya pranali mein annolet sakriyan mode aur alkine sakriyan mode key sanyojan kaa pratinidhitva kartaa haye. aam taur parr, ack kathor, oxophilic dhaatu (key, naa, aejee) annolet oxygen koo sakriya karati haye, jabaki ack naram, carbophilic dhaatu (peedi, kyu, mo) alkine key saath samanvaya karati haye. halanki, kuchh udaharanon mein, pratyek dhaatu kii sateek bhoomika spasht naheen haye. udaaharan key liye, 2005 key ack adhyayan mein toste aitt all. paaya gayaa kii ack pee. dee. (ii) phosphine complexes aur vaaee. bee. (otf) key saath ack alkynil-jadey hue β-ketoester key upchaar ney sambandhit cyclopenton key liye asmamit cyclisation koo prabhaavit kiya. yeh prastaavit haye kii ack pee. dee.-annolet ack vaaee. bee.-sakriya alkine mein jodata haye, halanki alkine key pee. dee. sakriyan key liye bhee udaaharan haye.
kull sanshleshan mein anuprayog.
aeu-utprerit konia-annie pratikriyaon key vikas key baad, toste aur sahakarmiyon ney kshaariya praakritik utpaad lycopladine aeye kii or iss tarah key parivartan koo niyojit kiya. kieral cyclohexanone 1 seey shuru hocker, anone karyatmakta kii ack shrinkhala ney silil anole eather 2 koo konia-aine agradoot key roop mein diyaa. cyclisation koo prabhaavit karane key liye, 2 koo utprerak aucle (pee. aff. aich.) aur aeye. jee. bee. aff. key saath upchaarit kiya gayaa taaki ekal diasteriomer key roop mein uchch upaj mein vinail iodide 3 pradaan kiya jaa sakey. anu key shesh bhaag koo teen charanon mein puuraa kiya gayaa thaa taaki aathh charanon mein (+)-lycopladine aeye aur kull milakar 17 pratishat upaj mill sakey.
2012 mein, kairira aur anya. sanshleshit, laal shaiwal laurencia maijuskula seey alag ack helogenated terpene, aur upaant charan key roop mein aeu-utprerit konia-aine cyclisation koo niyojit kiya. saikil 6 seey 11 charanon mein silil anole eather 7 praapt karane key baad, joe swayam 4 aur anone 5 key beach ack dials-elder cyclodation kaa utpaad haye, lekhakon ney 65 pratishat upaj mein tricycle 8 dene key liye 7 seey 50 moll% ichavaren utprerak kaa vishay banaaya haye. iss yaugik koo phir exo-methylene key klorinikaran dwara vistrit kiya jaataa haye.
2020 mein, yang aur sahakarmiyon ney (+)-vihoencin key asmamit sanshleshan key dauran ack diasterioselective konia-aine pratikriya koo niyojit kiya, joe podocarpus totara seey sanrachanaatmak roop seey ghanaa terpanoid haye, jise pahali baar 2017 mein lii samooh dwara sanshleshit kiya gayaa thaa. vinailogus ester 9 koo pahali baar chhah charanon mein kieral konia-aine agradoot 10 mein karyatmak banaaya gayaa thaa. baad mein 10 key upchaar mein dee. aim. aiss. oh. mein tbook key saath saikil koo ekal diasteriomer key roop mein 83 pratishat mein 11 pratishat kii upaj dee gaee. iss yaugik koo taba 15 charanon mein (+)-vihoencin taka pahunchane key liye aathh atirikt parivartanon aur kull milakar 4 pratishat upaj kii aavashyakta thee.

