
sttille prathikaranam

jaivasamshleshanathil vyaapakamaayi upayogikkunna oru raasapravarthanamaan sttille prathikaranam. eee prathikaranatthil rund jaiva grouppukalude samyojanam ulppedunnu, avayilonnu oorgaanottin samyukthamaayi (oorgaanostaaneynukal ennum ariyappedunnu) vahikkunnu. vividatharam jaiva electrophylukal mattu coupling pankaalikku nalkunnu. pala paladium-catalised coupling prathikaranangalil onnaanu sttille prathikaranam.
trialcyltinil gadippichirikkunna aarr1 group saadhaaranayaayi vinail, aaril grouppukal ulppede sp2-hybridised aanu.
eee oorgaanostanneynukal vayuvinum eerppathinum sthirathayullavayaanu, eee reyejantukalil palathum vaanijyaparamaayi labhyamaan allengil saahitya maathrkayil ninnu samanvayippikkaan kazhiyum. ennirunnaalum, eee tinn reagentukal valare vishaamshamullavayaan. x saadhaaranayaayi oru halide, athaayath sii. ell, bii. aarr, allengil aii, ennittum triflateukal, sulphonettukal, phosphettukal thudangiya seudohylideukalum upayogikkaam. niravadhi avalokanangal prasidheekarichittundu.
charithram.
oorgaanottin reyejantukalumaayi aaril haalaidukalude paladium catalised kaplinginte aadya udaaharanam 1976 ll collin eebon report cheythu. eee prathikaranam dayaril uthppannathinte 7 muthal 53 sathamaanam vare nalki. eee prakriya 1977ll toshihiko mygitta vazhi alkail-tinn reyejantukalumaayi asail chlorideukal bandhippikkunnathilekku vyaapippikkukayum 53 muthal 87 sathamaanam vare kettoon uthppannam nalkukayum cheythu.
1977-ll, aaril (sii), asail (dii) haalaidukalumaayi alil-tinn reyejantukalude samyojanathekkurichulla kooduthal pravartthanangal migitta prasidheekarichu. paladium kaattalistilekku kudiyeraanulla alail grouppukalude kooduthal kazhivu kuranja thapanilayil prathikaranangal nadatthaan anuvadichu. aaril haalaidukalude vilavu 4 sathamaanam muthal <aii. dii. 1> vareyum asail haalaidukalude vilavu 27 sathamaanam muthal 86 sathamaanam vareyumaanu. maigittayudeyum kosugiyudeyum aadyakaala sambhaavanakale prathifalippikkunna sttille prathikaranatthe chilappol mygitta-kosugi-sttille coupling ennu vilikkunnu.
1978ll joonn kenneth sttille, valare mikacha vilavu (76%-99%) labhikkuna neriya prathikarana saahacharyangalil niravadhi aaril, asail haalaidukal ennivayumaayi vividatharam alkail tinn reactors samyojippichathayi report cheythu. eee vishalavum soumyavumaaya prakriya upayogichu 1980-kalil niravadhi kettonukalude samanvayathekkurichulla thante pravartthanam sttille thudarukayum eee parivarthanatthinulla oru samvidaanam vyakthamaakkukayum cheythu.
1980kalude madhyathode, tinn ulppedunna coupling prathikaranangal enna vishayathekkurichulla 65 ladhikam prabandhangal prasidheekarikkukayum eee prathikaranatthinte substrate vyaapthi paryavekshanam cheiyunnathu thudarukayum cheythu. eee mekhalayile prarambha gaveshanam alkail grouppukalude samyojanathil shradha kendreekarikkumbol, bhaaviyile mikka pravarthanangalilum vinail, alcanyl, aaril, alail oorgaanostaaneynukal enniva haalaidukalaayi kooduthal krithrimamaayi upayogapradamaaya samyojanam ulppedunnu. eee oorgaanottin riyejantinte vaayuvilekkulla sthirathayum avayude synthesis eluppavum kaaranam, oorgaanik synthesisil sttille prathikaranam saadhaaranamaayi.
samvidaanam.
sttille prathikaranatthinte samvidaanam vipulamaayi padikkappettittund. kaattalitik sykkilil oru paladium kaattalistilekku oru halide allengil seudohalide (2) auxidative kootticherkkal (1), oru oorgaanottin riyejant upayogichu 3 traansmettaleshan (4), 5 nte reductive elemination enniva ulppedunnu.
ennirunnaalum, sttille kaplinginte vishadamaaya samvidaanam valare sankeernamaanu, koodaathe niravadhi prathikarana paathakaliloode sambhavikkam. mattu paladium-catalised coupling prathikaranangaleppole, sajeeva paladium kaattalist oru 14-electron pii. dii (0) complexanennu vishwasikkappedunnu, ithu vividha reethikalil srishtikkaan kazhiyum. 18-allengil 16-electron pii. dii. (0) srothassinte upayogam, sajeeva inam roopappeduthunnathinu ligand vighadanathinu vidheyamaakum. randaamathaayi, ligandless palediyathil (0) phosphinukal cherkkaam. avasaanamaayi, chithram pole, oru pii. dii. (ii) srothass (8),, muthalaayava kuraykkuka.) cherttha phosphine ligandukal allengil oorgaanottin reagentukal ennivayum saadhaaranamaanu.
auxidative kootticherkkal.
14-electron pii. dii. (0) complexilake auxidative kootticherkkal nirddeshikkappedunnu. eee prakriya 16 electron pii. dii. (ii) inam nalkunnu. oesi polulla ionic ligandukal [pidi (oesi) (pr3) enn]-roopeekaranathiloode eee ghattathe thwarithappeduthukayum ithu paladium inathe kooduthal nucleophillic aakkukayum cheiyunnuvennu abhipraayamund.
chila sandarbhangalil, prathyekichu oru sp3-hybridised organohalide upayogikkumbol, oru sn2 tharam samvidaanam prabalamaanu, ennirunnaalum ithu saahithyathil saadhaaranayaayi kaanapedunnilla.
ennirunnaalum, saadhaaranayaayi oru samyojitha auxidative kootticherkkalinushesham oru "sis"-intermediat roopappettaalum, eee uthppannam athinte "trans"-isomerumaayi athivega santhulithaavasthayilaanu.
isomerisation ivide eshtappedunnathinu niravadhi kaaranangalund. onnamathaayi, phosphinukal polulla eee prakriyakalil saadhaaranayaayi oru valia ligand settu upayogikkunnu, parasparam thaarathamyappeduthumbol "sis" ooriyanteshan sweekarikkunnathu avarkk valare prathikoolamaanu, ithu kooduthal anukoolamaaya trans uthppannathilekku isomerisation undaakkunnu. eee prathibhaasathinu oru badal vishadeekaranam, antisymbiosis allengil transphobia ennu vilikkappedunnu, sdn modalinte aahvaanamaanu. eee sidhaanthathinu keezhil, paladium oru hypervaalant speesheesaanu. athinaal r1 umm trans ligand parasparam trans cheiyunnathinaal, bandhatthinaayi oru paladium oorbitalumaayi malsarikkum. paladium bhramanapathathinaayi valareyadhikam malsarikkunna rund sakthamaaya sambhavana grouppukal undaakumbol eee 4-electron 3-sentar boond ettavum durbalamaanu. saadhaaranayaayi upayogikkunna eathoru ligandumaayum thaarathamyappeduthumbol, sii-donner aarr 1 ligandinu valare uyarnna trans ephakt undu. eee trans swaadheenam malsaraadhishtitha ligandukal parasparam engane pallaadiyatthinte bhramanapathathinaayi malsarikkum ennathinte alavaanu. saadhaarana ligand settu, phosphine, sii-donors (aarr 1) enniva mriduvaaya ligandukalaanu, athaayath avaa palediyavumaayi sakthamaaya bondukal roopappeduthukayum bondinginaayi parasparam valareyadhikam malsarikkukayum cheyyum. haalaidukalo seudohalideukalo ganyamaayi kooduthal electronegative aayathinal, palediyavumaayulla avayude bandham valare dhruveekarikkappedum, ex groupile electron saandrathayude bhooribhaagavum avaye kuranja trans ephakt ligandukalaayi maattunnu. athinaal, r1 groupinu palediyavumaayi sakthamaaya oru boond roopappeduthaan kazhiyumennathinaal r1 trans tuu x aakunnath valare anukoolamaayirikkum.
traansmettaleshan.
auxidative addition ghattathil ninnu "trans" intermediattinte traansmettaleshan substrateukaleyum avasthakaleyum aashrayich vividha samvidaanangaliloode munnott pookumennu vishwasikkappedunnu. sttille kaplinginulla ettavum saadhaaranamaaya traansmettaleshan oru associative mechanism ulkkollunnu. eee paatha soochippikkunnathu saadhaaranayaayi oru alail, alkenyl allengil aaril grouppumaayi bandhippichirikkunna oru tinn aattamaaya oorgaanostaaneynu eee eratta bondukalilonnu vazhi palediyavumaayi ekopippikkaan kazhiyum ennaanu. ithu 18 electron speesheesukalulla oru pentaavalant inathe srishtikkunnu, avaykku pinneedu ligand verpiriyaliloode veendum oru chathuraakrithiyilulla planner complexes roopeekarikkaan kazhiyum. oorgaanostanneyn r2 grouppiloode palediyavumaayi ekopippikkappedunnum, r2 aupachaarikamaayi palediyathilekku mattanam (r2-sn boond thakarkkanam), koodaathe x group tinninotoppam pookukayum traansmettaleshan poortthiyaakkukayum venam. rund samvidaanangaliloodeyaanu ithu sambhavikkunnathenn vishwasikkappedunnu.
onnamathaayi, oorgaanostaanan thudakkathil trans mettal complexilake cherkkumbol, x groupinu palediyathinu purame tinnumaayi ekopippikkaan kazhiyum, ithu oru chaakrika parivartthana avastha srishtikkunnu. eee adakttinte thakarcha r3sn-x nashtappedunnathinum oru "sis" bandhatthil r1, r2 ennivayulla oru trikonamithi paladium complexinum kaaranamaakunnu. mukalil kaanunnathupole "trans" paladium complexilake oorgaanostaaneyn cherkkunnath ulppedunna mattoru saadhaarana samvidaanamaanu; ennirunnaalum, eee saahacharyathil, x group tinnumaayi ekopippikkunnilla, ithu oru thuranna parivartthana avastha srishtikkunnu. tinninumaayi bandhapetta α-kaarban palediyathe aakramichathinusesham, tinn complexes oru nettu positteev charjumaayi purappedum. chuvadeyulla schemil, tinnumaayi ekopippikkunna eratta boond r2 neey soochippikkunnuvennu dayavaayi shradhikkuka, athinaal eathenkilum alcanyl, allail allengil aaril group. koodaathe, ex groupinu mekkaanisathinidayil eppol verpiriyaanum avasaanam sn + complexumaayi bandhippikkanum kazhiyum. saandrata pravartthana sidhaantha kanakkukoottalukal pravachikkunnath 2 ligandukal palediyathil gadippichirikkukayum x group vidukayum cheythaal oru thuranna samvidaanam nilanilkkumennu, athesamayam traansmettaleshan munbu oru ligand verpiriyukayaanenkil chaakrika samvidaanam kooduthal saadhyathayullathaanu. athinaal, dhruva laayakangalile triflateukal polulla nalla leaving grouppukal aadyathethinu anukoolamaanu, athesamayam bulky phosphine ligandukal randaamathethinu anukoolamaanu.
oru desosiative allengil solvant assisted mekkaanisathiloodeyaanu traansmettaleshan kuravaaya oru saadhaarana paatha. ivide, tetraavalant paladium inathil ninnulla oru ligand verpiriyunnu, oru ekopana laayakathin palediyathilekku cherkkaan kazhiyum. layakam verpett 14-electron trivalent intermediat roopappedumbol, oorgaanostaaneynu palediyathilekku cherkkaan kazhiyum, mukalil paranjathupole oru thuranna allengil chaakrika tharam prakriyaykku vidheyamaakum.
reductive elemination steppu.
aarr1-aaar2 kuraykkunnathinu, eee grouppukal paraspara "sis" ekopana sittukal kaivashappedutthanam. athinaal eathenkilum "trans"-aadktukal "sis" intermediattilekku isomerise cheyyanam allengil coupling nirashamaakum. reductive elimineshanaayi vividha samvidaanangal nilavilundu, iva saadhaaranayaayi samyojithamaayi kanakkaakkappedunnu.
aadyam, traansmettaleshan ghattathil ninnulla 16-electron tetraavalant intermediattinu oru square planner complexil ninnu sahayamillaathe reductive elemination vidheyamaakaam. eee prathikaranam rund ghattangalilayi sambhavikkunnu aadyam, reductive elimineshane thudarnnu lohavumaayi puthuthayi roopamkonda sigma bondinte ekopanam, athyanthikamaaya viyojip enniva jodicha uthppannam nalkunnu.
ennirunnaalum, munbathe prakriya chilappol mandagathiyilullathaanu, koodaathe 14-electron tii aakruthiyilulla intermediat nalkunnathinu oru ligand verthirikkunnathiloode ithu valareyadhikam thwarithappeduthaam. eee intermediattinu pinneedu oru vaii-aakruthiyilulla adakt roopappeduthunnathinaayi punakrameekarikkan kazhiyum, ithu vegathil reductive elemination vidheyamaakum.
avasaanamaayi, oru adhika ligantinu pallediyavumaayi bandhappedutthi 18-electron trikona bipyramidal ghadana roopeekarikkaan kazhiyum, bhoomadhyarekhayile sthaanangalil r1, r2 sis enniva parasparam bandhippikkunnu. eee intermediattinte jyamiti athine mukalilulla y aakruthiyumaayi saamyamullathaakkunnu.
valia ligandukalude saannidhyavum illaathaakkal nirakk vardhippikkum. valia kadiyetta konukalulla phosphines polulla ligandukal l, r1, r2 ennivaykkidayilulla sterik vikarshanathinu kaaranamaakunnu, athinte falamaayi l, r grouppukal thammilulla koonn vardhikkukayum r1, r2 ennivaykkidayilulla koonn kurayukayum cheiyunnu, ithu vegathil kuraykkaan anuvadikkunnu.
chalanathmakatha.
oorgaanostanneyinukal paladium kaattalistukalumaayi traansmettalett cheiyunna nirakk chuvade kaanichirikkunnu. tinnil gadippichirikkunna sp2-hybridised kaarban grouppukalaanu ettavum saadhaaranayaayi upayogikkunna coupling pankaalikal, sp3-hybridised kaarbanukalkk kadinamaaya avasthakal aavasyamaanu, koodaathe terminal aalkkainukal sonogashira prathikaranatthiloode oru sii-echu boond vazhi jodiyakkaam.
oorgaanik tinn samyukthamenna nilayil, oru trimethylstaanail allengil tributilstaainal samyuktham saadhaaranayaayi upayogikkunnu. trimethylstaanail samyukthangal tributilestainal samyukthangalumaayi thaarathamyappeduthumbol uyarnna prathipravartthanam kaanikkukayum valare lalithamaaya 1 echu-enmr spectra undaayirikkukayum cheiyunnuvenkilum aadyathethinte vishaamsham valare valuthaanu.
uyarnna vilavum vittuvarav nirakkum upayogichu prathikaranam nadathunnathil eathu ligandukalaanu ettavum nallathennu opttimais cheiyunnathu budhimuttaayirikkum. auxidative kootticherkkalinu electron sambannamaaya oru loham aavasyamullathinaal electron sambhavana cheiyunna ligandukale ithu anukoolikkunnu. ennirunnaalum, electroninte kurravulla oru loham transmetaleshanum reductive elemination gattangalkkum kooduthal anukoolamaanu, ithu electron pinvalikkunna ligaandukale ivide mikachathaakkunnu. athinaal, opttimal ligand settu vyakthigatha substrateukaleyum upayogichirikkunna avasthakaleyum valareyadhikam aasrayichirikkunnu. ivaykku nirakk nirnnayikkunna ghattatheyum traansmettaleshan ghattathinulla samvidaanatheyum maattaan kazhiyum.
saadhaaranayaayi, phosphine polulla intermediat donisittiyude ligandukal upayogikkunnu. trai-2-furilfosphine allengil triphenylarsenin polulla mithamaaya electron-paavar ligandukal upayogikkumbol nirakk mechappeduthalukal kaanaan kazhiyum. athupole, uyarnna daathaakkalude samkhyayulla ligandukalkku coupling prathikaranangale mandagathiyilaakkaano thadayaano kazhiyum.
eee nireekshanangal soochippikkunnathu saadhaaranayaayi, sttille prathikaranatthinte nirakk nirnnayikkunna ghattam traansmetaleshanaanu ennaanu.
aditteevukal.
sttille prathikaranatthile ettavum saadhaaranamaaya additteev stoikiyometrik allengil qoo-kaattalitik copper (i) aanu, prathyekichu copper iodide, ithu nirakk 103 madangu vardhippikkum. dhruva layakangalil copper oorgaanostaaneynumaayi traansmettalett cheiyunnuvennu sidhaanthamundu. thathfalamaayundaakunna oorgaano kappett reactorinu pinneedu paladium kaattalist upayogichu traansmettalett cheyyaan kazhiyum. koodaathe, eetheriyal layakangalil, pii. dii. sentarine sajeevamaakkunna oru phosphine ligand neekkam cheyyaanum chembinu kazhiyum.
x group palediyathil ninnu verpiriyunna sandarbhangalil lythium chloride sakthamaaya nirakk aaksilarantaanenn kandethiyittundu.iii. thuranna samvidaanam). chloride ayoon onnukil x groupine palediyathil sthaanabhrashtamaakkunnave vishwasikkappedunnu, ithu kaattalisttine traansmettaleshan kooduthal sajeevamaakkunnu allengil auxidative kootticherkkal thwarithappeduthunnathinna pii. dii. (0) adakttumaayi ekopippikkunnu. koodaathe, lickle uppu laayakathinte dhruveeyatha vardhippikkukayum ithu saadhaaranayaayi ionic ligandinu (-cl,-br,-otf muthalaayava) eluppamaakkukayum cheiyunnu.) pookuvaan. thf polulla oru layakam upayogikkumbol eee additteev aavasyamaanu; ennirunnaalum, enmp polulla kooduthal dhruveeya laayakathinte upayogam eee uppu aditteevinte aavasyakathaye mattisthaapikkum. ennirunnaalum, chakra samvidaanathiloode kaplinginte traansmettaleshan ghattam munnott pookumbool, lythium chloride cherkkunnath yadhaarthathil nirakk kuraykkum. chaakrika samvidaanathilennapole, phosphine polulla oru neutral ligand ionic x groupinu pakaram verpiriyanam.
avasaanamaayi, seesiyam fluoride polulla fluoride ayonukalude uravidangalum kaattalatik saikiline badhikkunnu. onnamathaayi, lythium chloridinte athe falathaal fluoridine oorgaanotriflettukale prathikaranangalude nirakk vardhippikkaan kazhiyum. koodaathe, fluoride ionukalkku tinn upolppannangalkk thottippanikkaraayi pravartthikkaan kazhiyum, ithu filtration vazhi avaa neekkam cheiyunnathu eluppamaakkunnu.
malsarikkunna side prathikaranangal.
sttille prathikaranavumayi bandhapetta ettavum saadhaaranamaaya side reactivity oru r2-r2 diamer roopappeduthunnathinaayi staanen reyejantukalude homo coupling aanu. saadhyamaaya rund samvidaanangaliloode ithu munnott pookumennu vishwasikkappedunnu. onnamathaayi, oorgaanostaaneyninu thulyamaaya rund gadakangal pii. dii. (ii) precatalistumaayi prathikarikkunnath reductive elimineshanushesham homocapled uthppannam nalkum. randaamathaayi, pii. dii (0) kaattalistin diamer nalkunnathinu oru samoola prakriyaykku vidheyamaakaam. saadhaaranayaayi kaimaattam cheyyappedenda sp2-hybridised group moonnu "kaimaattam cheyyappedaattha" alkail grouppukalum ulkkollunna parambaraagathamaayi tinnil tetraavalant aanu upayogikkunna oorgaanostaaneyn reactor. mukalil kandathupole, alkail grouppukal saadhaaranayaayi paladium kaattalistilekku kudiyerunnathil ettavum mandagathiyilaanu.
50 digri selshyas vare kuranja thapanilayil, palediyathileyum ekopitha phosphinileyum aaril grouppukalkku kaimaattam cheyyaamennum kandethiyittundu. saadhaaranayaayi kandethaanaakunnillengu, avaa pala kesukalilum oru cheria ulppannamaakaam.
avasaanamaayi, apoorvavum anyadeshavumaaya oru paarshwapravartthanathe sini substitution ennu vilikkunnu. ivide, oru aaril halaidinte prarambha auxidative kootticherkkalinushesham, eee pii. dii-aarr inathinu oru vinail tinn eratta bondil udaneelam cherkkaan kazhiyum. β-hydride elemination, migratory insersion, protodestaanileshan ennivaykku sesham, 1,2-disbsepteeted olephin samanvayippikkaan kazhiyum.
mattu niravadhi paarshwapravartthanangal sambhavikkam, ivayil iii/isad isomerisation ulppedunnu, ithu oru aalkkanailstanan upayogikkumbol oru prasnamaakaam. eee parivartthanatthinte samvidaanam nilavil anjjaathamaanu. saadhaaranayaayi, oorgaanostaaneyinukal jalavishleshanathinu valare sthirathayullavayaanenkilum valare electron sambushtamaaya aaril staaneyinukal upayogikkumbol, ithu oru pradhana paarshwapravartthanamaayi maarum.
vyaapthi.
electrophyl.
sttill prathikaranatthile saadhaarana coupling pankaalikalaanu vinail haalaidukal, itharathilulla prathikaranangal niravadhi prakrithi uthppannangalude motham sinthasisukalil kaanapedunnu. saadhaaranayaayi vinail iodideukalum bromideukalum upayogikkunnu. pii. dii. yilek (0) oxidative kootticherkkalinodu vinail chlorideukal vendathra prathikarikkunnilla. iodideukal saadhaaranayaayi eshtappedunnu avaa saadhaaranayaayi bromideukalekkaal vegathilum soumyamaaya saahacharyangalilum prathikarikkum. vinail bromaidinte saannidhyathil oru vinail iodide thiranjeduttha samyojanathiloode eee vyathyasam chuvade prakadamaakkunnu.
saadhaaranayaayi, kadinamaaya prathikarana saahacharyangalilozhike, prathikaranatthiludaneelam aalkkeeninte stereochemistry nilanirthunnu. vividatharam alkeenukal upayogikkaam, ivayil α-, β-haalo-α, β ansaachurettad kettonukal, esttarukal, sulfoxideukal (saadhaaranayaayi munnott pookaan chembu (i) additteev aavasyamaanu) ennivayum athilereyum ulppedunnu (chuvadeyulla udaaharanam kaanuka). vinail triflateukalum chilappol upayogikkunnu. chila prathikaranangalkk likel cherkkendathundu, mattullava mandagathiyilaakunnu, ithu rund yanthra pathakal undennu soochippikkunnu.
aaroyil, heterocyclic haalaidukal ennivayaanu saadhaarana electrophylukalude mattoru vibhaagam. vinail substrateukale sambandhichidatholam, bromideukalum iodideukalum avayude kooduthal chelavu undaayirunnittum kooduthalaayi kaanapedunnu. electron sambhavana cheiyunna pakarakkar, bayaaril valayangal ennivayum athilereyum upayogichu maattisthaapikkappett valayangal ulppede niravadhi aaril grouppukal thiranjedukkaam. pyridinukal, furence, theophenes, thayasolukal, indolukal, imidaasolukal, purinukal, yooraasil, cytosins, pyrimedines ennivayum athilereyum ulppede (hettarosaikkilukalude pattikaykkaayi chuvade kaanuka; oronnilum vividha sthaanangalil haalojanukalkk pakaram vaykkaam).
purinukal polulla nucleosideukalude hettarosaikkilukalil sankeernnatha srishtikkunnathinu sttille coupling upayogikkunnathinte oru udaaharanam chuvadeyundu. 
aaril triflateukalum sulphonettukalum vaividhyamaarnna oorgaanostaanen reactorukalumaayi jodiyaakkunnu. sttille prathikaranatthil triflateukal bromideukalumaayi thaarathamyappeduthumbol prathikarikkunnu.
asail chlorideukal coupling pankaalikalaayum upayogikkunnu, koodaathe keetonukal uthppaadippikkunnathin oorgaanostaaneyn, alkail-tinn reagentukal ennivaykkoppam polum ithu upayogikkaam (chuvadeyulla udaaharanam kaanuka). ennirunnaalum, sensitiivu functional grouppukalulla valia thanmathrakalaayi asail chloride functional grouppukal avatharippikkunnath chilappol budhimuttaanu. eee prakriyaykku vikasippichedutha oru badal sttille-carbonylative cross-coupling prathikaranamaanu, ithu kaarban monoxide ulppeduthaliloode carbonyl groupine avatharippikkunnu.
alylic, benzylic, propergillic haalaidukal ennivayum jodiyakkaam. saadhaaranayaayi upayogikkumbol, allilic haalaidukal oru η3 parivartthana avasthayiloode munnott pookunnu, ithu oorgaanostaaneyumaayi α allengil γ sthaanathu bandhippikkaan anuvadikkunnu, ithu pradhaanamaayum kuranjathu pakaramulla kaarban aanu (chuvadeyulla udaaharanam kaanuka). alcanyl epoxideukalkkum (aduthulla epoxideukalum aalkkinukalum) epoxide oru alcoholilekku thurakkunna athe η3 parivartthana avasthayiloode eee samyojanathinu vidheyamaakaam. allilic, benzylic asattettukal saadhaaranayaayi upayogikkumbol, propargelic asattettukal oorgaanostaananukalumaayi prathikarikkunnilla.
staanan.
oorgaanostaaneyn reactors saadhaaranamaanu. avayil palathum vaanijyaparamaayi labhyamaan. trialkkailttin chlorideukalumaayulla grignard allengil oorganolithiyam reagentinte prathikaranatthiloode staanen reagentukale samanvayippikkaan kazhiyum. udaaharanathinu, vinailmagneeshyam bromide tributin chlorideumaayi prathipravarthichaanu vinailtributiltintint thayyarakkunnathu. alkkainukaludeyo alkkinukaludeyo hydrostaanilation niravadhi derivateevukal nalkunnu. oorgaanottin reagentukal vaayuvum eerppavum sthirathayullavayaanu. chila prathikaranangal vellathil polum sambhavikkam. chromatography vazhi avaa shudheekarikkaan kazhiyum. mikka pravartthana grouppukalodum avar sahishnutha pulartthunnu. chila oorgaanottin samyukthangal valareyadhikam vishaamshamullavayaan, prathyekichu trimethylstaanail derivateevukal.
vinailstaaneyn allengil alkenylstaaneyn reyejantukalude upayogam vyaapakamaanu. parimithikale sambandhichidatholam, valare valia staanan reagentukalum α-carbonil pakaramulla staanaanukalum mandagathiyil prathikarikkukayo opttimaiseshan aavashyappedukayo cheiyunnu. udaaharanathinu, chuvadeyulla saahacharyathil, α-pakaramulla vinailstaanan sterik thadassam kaaranam oru terminal iodidemaayi maathrame prathikarikkukayulloo. 
arilstaaneyn reactorukalum saadhaaranamaanu, electron sambhavana cheiyunnathum electron pinvalikkunnathumaaya grouppukal yadhaarthathil traansmettaleshan nirakk vardhippikkunnu. traansmettaleshante rund samvidaanangal sambhavikkaamenn ithu veendum soochippikkunnu. eee reactorukalude eaka parimiti methyl grouppukalkku prathikarana nirakk kuraykkaan kazhiyunnathra cheruthaaya oortho-positionilulla pakarakkaraanu. vaividhyamaarnna hettarosaikkilukal (electrophyl vibhaagam kaanuka) coupling pankaalikalaayum upayogikkaam (chuvadeyulla tayasol valayamulla udaaharanam kaanuka).
staannanukalil ettavum prathipravartthanakshamaya alkkainailstannanukalum sttille couplingukalil upayogichittundu. terminal aalkkainukalkk sonogashira coupling vazhi avayude sii-echu bondiloode palledium kaattalistukalumaayi nerittu bandhippikkaan kazhiyumennathinaal avaa saadhaaranayaayi aavasyamilla. allailstannanukal pravarthichathaayi report cheyyappettittunde allilic haalaidukaleppole α, γ kootticherkkalukalude rejiyoselektivitti niyanthrikkunnathil budhimuttukal undaakunnu. sttille couplingukalil disttanen, asail staanen reagentukalum upayogichittundu.
aaplikkeshanukal.
vividha polymerukalude samanvayathil sttille prathikaranam upayogichittundu. ennirunnaalum, sttille prathikaranatthinte ettavum vyapakamaaya upayogam jaiva sinthasisukalilum prathyekichu prakrithi uthppannangalude synthesisilum upayogikkunnu.
prakrithi uthppannathinte motham synthesis.
laari ovarmaante quadrisemine siyude 19-ghatta enancioselective motham samanvayathil eratta sttill cross metathasis prathikaranam ulppedunnu. sankeernamaaya oorgaanostaaneyn rund aaril iodide grouppukalaayi bandhippichirikkunnu. eratta heck cyclisationushesham, uthppannam kaivarikkunnu.
paanekkinte 32 steppu anantioselective total synthesis oof ansamycin antibiotic (+)-micotrionol oru lettu steju taandam sttille type macrocycle coupling upayogikkunnu. ivide, oorgaanostaaneynil rund terminal tributile tinn grouppukal oru aalkkeenil akramikkunnu. eee oorgaanostaaneyn leanier starting metteeriyalinte rund attangalum oru macrocyclilekku "thunnunnu", eee prakriyayil kaanathaaya rund methylene unitukal cherkkunnu. seric amonium naitrettu (qaan) upayogichu sugandha coor ookseekarikkukayum hydrophluric assid upayogichu apasaranam cheyyukayum cheytha sesham moonnu ghattangalilayi 54 sathamaanam vilavil prakrithi uthppannam labikkum.
 steefan eph. martin, sahapravarthakar ennivarude 21 steppu anantioselective total synthesis oof mansamine aantittoomar alcaloid irsinal eiii oru taandam vann-pottu sttille/dials-alder prathikaranam upayogikkunnu. vinail bromydelake oru alkeen group cherkkunnu, thudarnnu pyrolidine valayathile alkeen alkeen thammilulla "inn sittu" dials-alder cyclododition.
oxasolomycin, lancasidine sii, onamide eiii, kaalikulin eiii, lepisidine eiii, repostaattin eiii, lucilactain ennivayulppede niravadhi motham synthesisukal sttille prathikaranam upayogikkunnu. chuvadeyulla chithram anthima prakrithi ulppannamaaya organohalide (neela), oorgaanostaaneyn (chuvapp), roopappedunna boond (pachayum vrithaakruthiyilullathum) enniva pradarshippikkunnu. eee udaaharanangalil ninnu, sinthasisinte prarambha ghattangalilum (oxasolomycin, kalikulin eiii), oru kanverjant roottinte avasaanathilum (onamide eiii, lancasidine sii, repostaattin eiii), allengil madhyathilum (lepisidine eiii, lucilactain) sttille prathikaranam upayogikkaamenn vyakthamaan. repostaattin eyude samanvayathil rund kankarant sttill couplingukalum thudarnnu oru ring-clossing metatheesasum undu. loosilaakteyninte samanvayathil oru vashath boran maruvashathu staananum ulla oru madhya subunit undu, ithu thudarnnulla suzuki couplingine thudarnnu sttille prathikaranatthinu anuvadikkunnu.
vyathiyanangal.
vividha jaiva layakangalil prathikaranam nadathunnathinupurame, jaleeya laayakathil vishalamaaya sttill couplingukal anuvadikkunna avasthakal aavishkarichittundu.
kyoo (aii) lavanangalude saannidhyathil, paladium-oonn-kaarban oru phalapradamaaya uthejakamaanennu theliyikkappettittund.
pacha rasathanthrathinte mekhalayil mannittol polulla panchasaarayude kuranja urukunnathum uyarnna dhruveeyavumaaya mishrithathilum dimethyleria polulla yooriyayilum amonium chloride polulla uppilum oru sttille prathikaranam nadakkunnathaayi report cheyyappedunnu.
. kaattalist sisttam triphenylarsine aannu
sttille-carbonylative cross-coupling.
sttille couplingle oru saadhaarana maattam aarr 1 num aarr 2 num idayil oru carbonyl group samyojippikkuka ennathaanu, ithu kettonukal roopappeduthunnathinulla kaaryakshamamaya reethiyaayi varthikkunnu. oorgaanostanneyn asail chlorideukalumaayi bandhippikkunnathinte maigittayum sttillum (charithram kaanuka) nadatthiya prarambha paryaveshanavumaayi eee prakriya valare saamyamullathaan. ennirunnaalum, eee moyittikal ellaayppozhum eluppathil labhyamalla, prathyekichu sensitiivu functional grouppukalude saannidhyathil roopeekarikkaan prayaasamaan. koodaathe, avayude uyarnna prathipravartthanam niyanthrikkunnath velluviliyaakum. kaarban monoxide (qoo) anthareekshathil ozhike, sttille-carbonylative cross-coupling sttille kaplinginte athe avasthayaanu upayogikkunnathu. prarambha auxidative kootticherkkalinushesham koykk paladium kaattalistumaayi (9) ekopippikkaan kazhiyum, thudarnnu pii. dii-aarr 1 bondilekku (10) qoo insersion nadathukayum thudarnnu keetonilekku (12) thudarnnulla reductive elemination undaakkukayum cheiyunnu. traansmettaleshan ghattam saadhaaranayaayi nirakk nirnnayikkunna gattamaanu.
laari ovarmaanum sahapravarthakarum avarude 20-ghatta enancioselective motham stricknin synthesisil sttille-carbonylative cross-coupling upayogikkunnu. cherttha carbonyl pinneedu oru vittig prathikaranatthiloode oru terminal aalkkeenaayi parivartthanam cheyyappedunnu, ithu oru aasa-koppu-maanikk prathikaranatthiloode pradhana thritheeya naitrajan pentacyclic korum roopappedaan anuvadikkunnu.
georgio oorttaar thudangiyavar. benzophenon phosphorukalude samanvayathinu sttille-carbonylative cross-coupling engane upayogikkaamenn paryavekshanam cheythu. iva 4-benzoil-ell-fenilalanine pepttaidukalil ulcherkkukayum vividha pepttaid-protein edapedalukal paryavekshanam cheiyunnathinaayi avayude photoaphinity labeling gunangalkkayi upayogikkukayum cheythu.
luis hegedesinte 16-ghatta racemic motham jaatraphon synthesis 11-anga macrocycle roopeekarikkunnathinulla avasana ghattamayi oru sttille-carbonylative cross-coupling ulppedunnu. oru halide pakaram, oru vinail triflate avide coupling partneraayi upayogikkunnu.
sttille-kellie coupling.
aarilhalaidukalil ninnum distannanukalil ninnum aarilstannanukale roopappeduthunna 1976-ll eebon prasidheekaricha seminal prasidheekaranam upayogichu, tii. rooss kellie eee prakriya arilhalaidukalude intramolecular couplingle prayogichu. eee taandam staanileshan/aaril halide coupling vividatharam dihydrophenanthreneukalu samanvayathinaayi upayogichu. roopappetta aantharika valayangalil bhooribhaagavum 5 allengil 6 amgangalil parimithappedutthiyirikku, ennirunnaalum macrocyclisationte chila kesukal report cheyyappettittund. oru saadhaarana sttill couplingle ninnu vyathyasthamayi, chlorin oru halojanaayi pravarthikkunnilla, orupakshe halojan shreniyile kuranja prathipravartthanam kaaranam (athinte hrasvamaaya boond neelavum sakthamaaya boond desosiation oorjjavum auxidative aditioniloode takarkkaan kooduthal budhimuttaakkunnu). thaazhe koduthirikkunna skeeminte madhyathil aarambhich gadikaaradishayil pookunna palledium kaattalist (1) auxidative aayi ettavum reactive sii-ex bondilekku (13) cherthu 14 roopappeduthunnu, thudarnnu distaaneynumaayi (15) traansmettaleshan cheyth 16 roopavum reductive elemination vazhi oru arilstaaneyn (18) roopappedukayum cheiyunnu. punarulppaadippicha paladium kaattalist (1) nuu auxidative 18 nte randaamathe sii-ex bondilekku cherthu 19 roopeekarikkaan kazhiyum, thudarnnu intramolecular traansmettaleshan 20 vilavu nalkunnu, thudarnnu koottiya uthppannam (22) nalkunnathinu reductive elemination.
jee jacq lye thudangiyavar. vividatharam benzo [4,5] furopyridines ring sisttangalude samanvayathil sttille-kellie coupling upayogichu. avar oru moonnu ghatta prakriya aarambikkunnu, athil oru bookwald-hartwig amination, mattoru paladium-catalised coupling prathikaranam, thudarnnu oru intramolecular sttille-kellie coupling enniva ulppedunnu. aaril-iodide boond aril-bromide bondukalekkaal vegathil palediyathilekku auxidative aayi cherkkumennu shradhikkuka.

