12.4.1 Radikaalisyklisaatio
Vinyylihalogeeni 8.12 (0,5 mmol) liuotettiin 50 ml:aan kuivaa tolueenia argonkaasukehän alla.
Liuos lämmitettiin refluksoitumispisteeseen asti, jonka jälkeen liuokseen lisättiin tipoittain tributyylitinahydridi (0,20 ml, 98 %, 0,6 mmol, 1,2 ekviv.), ja AIBN (17,1 mg, 0,1mmol, 0,2 ekviv.) liuotettuna pieneen määrään tolueenia. Reaktioseoksen annettiin refluksoitua, kunnes lähtöainetta ei ollut enää jäljellä. Reaktioseoksen annettiin jäähtyä huoneenlämpöön, jonka jälkeen alipaineessa konsentroitu raakatuote puhdistettiin flash-kromatografisesti (EtOAc/n-heksaani 0:100 → 30:70). Tuotteita sisältäneet fraktiot yhdistettiin, konsentroitiin alipaineessa ja karakterisoitiin NMR-spektroskopian avulla.
12.4.2 Ru-katalysoitu syklisaatio
Vinyylienyyni 8.13 (0,2 mmol) liuotettiin kuivaan tolueeniin (80 ml) ja lämmitettiin 50 °C, jonka jälkeen seokseen lisättiin [CpRu(MeCN)3]PF6 (4,9 mg, 0,01 mmol, 0,1 ekviv.). Reaktio sammutettiin trietyyliamiinilla (0,25 ml), kun reaktioseos oli jäähtynyt huoneenlämpöiseksi.
Seos suodatettiin ohuen celite-kerroksen läpi, konsentroitiin alipaineessa ja karakterisoitiin NMR-spektroskopian avulla.
12.4.3 Pd-katalysoitu syklisaatio
Vinyylihalogeeni 8.12 (0,06 mmol) liuotettiin kuivaan asetonitriiliin (4 ml), jonne lisättiin palladium(II)asetaattia (1,8 mg, 0,01 mmol, 0,1 ekviv.), trifenyylifosfiinia (10,8 mg, 0,04 mmol, 0,7 ekviv,) ja kaliumkarbonaattia (23,5 mg, 0,2 mmol, 3,0 ekviv.). Seoksen annettiin olla huoneenlämmössä vuorokausi ja vuorokausi 60 °C. Reaktio sammutettiin ionivaihdetulla vedellä (10 ml). Vesifaasia pestiin DCM:llä (35 ml). Yhdistetyt orgaaniset faasit pestiin kylläisellä suolaliuoksella (15 ml) ja kuivattiin kidevedettömällä Na2SO4:lla. Alipaineessa kuivattu raakatuote karakterisoitiin NMR-spektroskopian avulla.
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LIITE 8: TPSH 8.8 13C NMR-spektri
LIITE 9: Halogeenialkoholin 7.13 1H NMR-spektri LIITE 10: Halogeenialkoholin 7.13 13C NMR-spektri LIITE 11: Vinyylihalogeenin 8.14 1H NMR-spektri LIITE 12: Vinyylihalogeenin 8.14 13C NMR-spektri LIITE 13: Vinyylihalogeenin 8.12 1H NMR-spektri LIITE 14: Vinyylihalogeenin 8.12 13C NMR-spektri LIITE 15: Enyynialkoholin 8.10 1H NMR-spektri LIITE 16: Enyynialkoholin 8.10 13C NMR-spektri LIITE 17: Vinyylienyynin 8.13 1H NMR-spektri LIITE 18: Vinyylienyynin 8.13 13C NMR-spektri
LIITE 19: Karteesinen koordinaatisto: makrolaktoni 7.6, konformeerit 1 ja 2 LIITE 20: Karteesinen koordinaatisto: makrolaktoni 10.1, konformeerit 1–4 LIITE 21: Karteesinen koordinaatisto: makrolaktoni 10.2, konformeerit 1 ja 2
1H-NMR 300 MHz
8.3
13C-NMR 75 MHz
8.3
1H-NMR 300 MHz
8.2
13C-NMR 75 MHz
8.2
1H-NMR 300 MHz
8.6
13C-NMR 75 MHz
8.6
1H-NMR 300 MHz
8.8
13C-NMR 75 MHz
8.8
1H-NMR 300 MHz
7.13
13C-NMR 75 MHz
7.13
1H-NMR 300 MHz
8.14
13C-NMR 75 MHz
8.14
1H-NMR 300 MHz
8.12
13C-NMR 75 MHz
8.12
1H-NMR 300 MHz
8.10
13C-NMR 75 MHz
8.10
1H-NMR 300 MHz
8.13
13C-NMR 75 MHz
8.13
Karteesinen koordinaatisto: Makrolaktoni 7.6
Konformeeri 1
H 6.97527054 5.47418658 8.35025287 C 7.88240427 6.08339996 6.49044376 C 9.64398462 7.71499083 6.65086405 H 10.97827090 5.28982446 6.90560897 C 11.13531860 7.48659420 7.02431611 C 6.57676382 8.36773288 7.90469785 H 6.05319213 4.99752183 6.86718755 H 7.56464410 10.08092145 4.98119446 O 8.82804029 6.68932887 7.30139794 H 9.42904992 9.86945079 6.45030434 O 8.00522352 5.91777028 5.28217129 C 8.98378411 9.05685011 7.05906539 C 7.47167260 9.02981218 6.84411200 C 5.80964874 7.09565706 7.45351907 H 7.17797351 8.13265404 8.80714476 H 12.41004591 7.24300477 8.78651304 H 4.99022130 6.90026235 8.17923677 H 5.81028552 9.11105485 8.21756452 H 9.19955836 9.27681275 8.12679108 H 10.70998579 6.73089598 9.04403352 H 11.13392005 8.47393938 9.00527534 H 9.53622126 7.58250693 5.55326163 C 11.35351404 7.48670037 8.55296375 H 11.81562708 8.63798371 5.27066023 H 11.79175578 9.58831087 6.79471808 C 11.99604786 8.58826064 6.36461914 H 13.07248485 8.37083611 6.51926155 H 11.41335607 6.07158266 5.35534659 C 11.56308009 6.11344868 6.45315086 H 12.63570425 5.92777592 6.66427719 H 5.32860067 7.28822643 6.47231542 C 6.65565478 5.79742409 7.33796734 C 6.93423974 9.59588947 5.74356437 H 5.84696190 9.59857146 5.56248149
Konformeeri 2
H 6.16939363 9.18828828 9.27400023 C 6.89914758 7.17933968 8.99208389 C 9.28581471 6.89117574 9.16127243 H 8.40788468 6.52725123 11.76557603 C 10.15247867 6.76279168 10.44114205 C 7.98800748 9.09491456 6.96222123 H 4.96848528 8.04022953 8.55117471 H 9.46382457 6.15234215 5.68212960 O 8.09395849 7.67930731 9.48612068 H 10.74054750 6.96151361 7.54704978 O 6.64793346 5.98908071 8.84678134 C 9.92541464 7.60049856 7.94186250 C 8.90482084 7.86727426 6.84091189 C 6.47320161 8.79508841 7.13662003 H 8.33472972 9.74354342 7.79341707 H 11.17506448 8.72496392 10.32420692 H 5.89388621 9.70661321 6.87297945 H 8.10097164 9.69384305 6.03217259 H 10.38169477 8.55947121 8.26698351 H 11.07220607 8.03566868 11.96623106 H 9.61632884 8.75553851 11.20499290 H 8.94073163 5.88047700 8.85565004 C 10.52273239 8.15026343 11.01069802 H 11.18681062 4.99338303 9.63568358 H 12.08836864 6.52523358 9.40239194 C 11.43263429 5.97007202 10.10083306 H 12.02230069 5.76914527 11.01794474 H 9.03438680 4.98524012 11.11238462 C 9.33248753 5.98222357 11.49474700 H 9.92871517 5.83614860 12.41786406 H 6.17497204 8.00684508 6.41392950 C 6.03307553 8.34925137 8.56012492 C 8.81104103 7.03489391 5.78227182 H 8.07973478 7.20290661 4.97473649
Karteesinen koordinaatisto: Makrolaktoni 10.1
Konformeeri 1
C 6.56102494 6.63169502 10.15146950 C 7.85886004 5.94884148 10.54977261 C 9.04382249 8.08274496 8.58305203 O 6.63302637 7.63129710 9.19469564 H 6.13931715 9.99666017 8.45120400 C 7.65442841 7.65816991 8.15060975 H 7.79518009 10.44532348 7.93453820 H 9.75489710 8.11142365 7.73782031 C 8.58015896 6.85057651 11.58426801 H 7.59814869 4.97601970 11.00653302 H 8.52016465 5.76859889 9.68101610 C 8.75700891 8.31497719 11.10887688 H 9.57230925 6.40179697 11.80626100 H 7.99630102 6.84488367 12.52940913 C 9.53942727 8.39311924 9.80436637 H 9.30240543 8.87605133 11.89727744 H 7.76424599 8.79634639 11.00795401 H 11.54213950 8.71507221 8.99036987 C 11.00083796 8.75479002 9.95456690 H 11.11011907 9.77722040 10.37706921 H 11.50843720 8.06730250 10.66701355 H 5.23772183 8.60719631 5.79882072 O 5.49985307 6.45649141 10.73635659 C 7.04485131 8.57947708 7.03569381 H 6.41474297 10.66536548 6.81049645 H 7.72308573 6.63025935 7.71567922 C 6.83753281 10.00414219 7.59257074 H 8.92919735 9.17319323 6.03250902 H 8.26240238 7.60118676 5.47618572 C 7.99332205 8.62290051 5.81736842 H 7.49460483 9.14006320 4.97391040 H 5.82885544 6.95705232 6.18021607 C 5.69215175 7.97946637 6.59085786 H 4.98239991 7.91581871 7.43550939
Konformeeri 2
C 10.07006594 5.77021076 6.25668822 C 11.21518676 5.68308122 7.24435822 C 9.01669678 8.47560180 5.86598596 O 8.96146722 6.29494675 6.90805309 H 7.58057991 7.22283407 8.89016497 C 8.17990217 7.23175509 6.10539783 H 7.61045381 8.91316901 8.27699168 H 8.68941190 9.07803209 4.99896409 C 11.82062848 7.10459397 7.40172925 H 10.84121513 5.32315827 8.22441380 H 11.97639294 4.98003788 6.85579123 C 10.78846219 8.21994133 7.74016200 H 12.36324073 7.36345306 6.46661605 H 12.57861481 7.05519499 8.21267763 C 10.12917348 8.88656565 6.52592288 H 11.33447871 9.01512275 8.29262220 H 10.03093106 7.81786338 8.43893472 H 10.40827658 10.57083348 5.15043407 C 10.85902541 10.13096692 6.06068345 H 10.86198589 10.90195809 6.86276097 H 11.92726922 9.90615419 5.84467744 H 6.63963631 5.32766006 7.41616166 O 10.13858068 5.55011656 5.05586649 C 6.81701179 7.44734450 6.83882496 H 6.05708337 8.15902727 8.76266748 H 7.97204620 6.76298524 5.11620123 C 7.03503512 7.96572645 8.27644715 H 6.43325132 9.48321030 6.06987817 H 5.84784408 8.17101956 4.99010714 C 5.97444065 8.47493408 6.05022479 H 4.96514717 8.55362332 6.50382091 H 5.08876696 6.23176455 7.40307380 C 6.05799045 6.10285588 6.88123135 H 5.84750110 5.72667201 5.85853870
Konformeeri 3
C 6.61597854 8.27822232 8.95571687 C 6.06612179 6.86646016 9.03979954 C 9.10152840 8.51939162 7.45328523 O 7.88049546 8.28021023 9.53239888 H 9.98488169 7.25773301 10.64762098 C 8.84757885 9.11659331 8.82380432 H 10.98460921 7.32876525 9.15840255 H 9.50220829 9.23972729 6.71695471 C 6.72334194 6.03331022 7.90161017 H 6.33065947 6.42351332 10.02241031 H 4.96422818 6.88453147 8.92442154 C 8.27933800 6.09437271 7.85005759 H 6.30592382 6.37672568 6.93087523 H 6.40568994 4.97706977 8.03375048 C 8.84734160 7.25731131 7.02489190 H 8.63660168 5.15393810 7.37644361 H 8.68171290 6.09273859 8.88020062 H 9.44132583 7.77525650 4.98276103 C 9.09252105 6.90542172 5.57108302 H 9.84727256 6.09434205 5.47938483 H 8.16300936 6.51912278 5.09695669 H 8.89812417 9.39549631 11.57744085 O 6.11383650 9.22496351 8.36343404 C 10.10005815 9.26024219 9.74147516 H 11.61429700 7.99602844 10.69657391 H 8.39910433 10.12736900 8.68964130 C 10.70228820 7.87883078 10.07761065 H 11.53715245 9.60491568 8.10127414 H 10.72340518 11.09458015 8.68601033 C 11.14979644 10.11961383 9.00239490 H 12.01140906 10.32444843 9.66916344 H 10.54098355 10.10764813 11.72009660 C 9.67336446 9.97618871 11.04131722 H 9.25344021 10.97967757 10.82377793
Konformeeri 4
C 5.73817152 8.19197092 8.76064113 C 5.98077246 6.84290171 8.07460434 C 8.66048456 8.95731779 8.43969565 O 6.28927427 9.33812890 8.21822080 H 6.79293913 11.81445867 8.20309518 C 7.55146199 9.24283994 7.45747554 H 8.58730976 11.82268254 8.22223439 H 9.06337774 9.81760069 8.99990933 C 7.17780994 6.02691397 8.61910937 H 5.05628293 6.27075695 8.28500018 H 6.05711521 6.95990431 6.97183587 C 8.57543031 6.44978037 8.10281985 H 7.00900794 4.96717726 8.32802200 H 7.15914936 6.05981585 9.73114771 C 9.11383141 7.72020575 8.75101980 H 9.28212967 5.61900146 8.31066818 H 8.54184602 6.55473893 6.99560860 H 11.06050993 7.01566809 9.41991840 C 10.15579123 7.51685140 9.82850763 H 10.46533895 8.47173934 10.29546843 H 9.76462438 6.85082159 10.62868636 H 6.58474521 11.56323134 5.03088585 O 5.00322380 8.29235807 9.73644403 C 7.69284701 10.56208407 6.63960600 H 7.71011188 12.72927851 6.95616011 H 7.46615278 8.41095208 6.72695459 C 7.69650964 11.80172732 7.56341312 H 9.89635063 10.41536888 6.50750079 H 9.02932730 9.60331376 5.16542140 C 9.01474265 10.48551674 5.83935308 H 9.13661447 11.38910723 5.20928941 H 6.47357844 9.77788003 4.97904506 C 6.50126430 10.65474083 5.65936905 H 5.53939574 10.69864486 6.20525067
Karteesinen koordinaatisto: Makrolaktoni 10.2
Konformeeri 1
C 9.13299969 6.20737439 8.11855263 C 10.49155398 5.75974933 8.65165878 C 10.47381419 8.76297946 7.04195200 O 8.69217606 7.26780145 8.89817657 H 6.45636806 9.82614958 10.85351667 C 8.19029442 8.42016712 8.13752362 H 9.84912154 9.51620420 8.99194072 H 9.09905832 10.33383349 7.59549207 C 11.41162163 7.01972861 8.69171286 H 10.37504668 5.33900854 9.67436175 H 10.89619768 4.97248375 7.98481642 C 11.34794196 7.77996061 7.37885360 H 11.09076877 7.66060809 9.53700707 H 12.45362385 6.69761698 8.90097457 H 12.02845938 7.41498019 6.58697353 C 9.42275115 9.34642946 7.98284957 H 7.83119318 8.67232141 10.87190542 H 9.43816069 9.19439881 5.18044891 O 8.54213031 5.78979404 7.13194494 H 11.18827887 8.84050581 4.98057543 C 6.96238423 9.00806371 8.88225022 H 8.06017879 10.34096754 10.26281242 H 7.85534182 8.04729800 7.14545097 C 7.35292526 9.48880605 10.29693445 H 6.14631258 9.87384955 7.02494616 H 5.44671040 10.55013360 8.53040822 C 6.38321767 10.18447451 8.06354031 H 7.07950001 11.04440656 8.01239366 H 5.61096088 7.50840430 7.98928983 C 5.89257162 7.89604495 8.98973782 H 6.26456344 7.04261969 9.58765676 H 4.97812307 8.28859415 9.47783225 C 10.44445727 9.32772706 5.63864808 H 10.64408030 10.42182726 5.64385344
Konformeeri 2
C 10.25046531 5.86793361 6.93470845 C 11.12642553 5.76217983 8.16630119 C 9.38379981 8.74263532 8.45041982 O 8.95404704 6.13220028 7.32591370 H 6.38461328 6.07164198 4.98137418 C 8.31992053 7.22859079 6.59167144 H 10.05773175 8.47250944 6.40759440 H 8.55954016 9.40382026 6.54662236 C 11.49674107 7.23312326 8.55191127 H 10.57509344 5.27377895 8.99484320 H 12.04685386 5.19425732 7.92652982 C 10.39119264 8.11643324 9.11519974 H 11.94042465 7.70760724 7.64836272 H 12.30948714 7.17832762 9.30495183 H 10.48011656 8.33251625 10.19592551 C 9.09796128 8.53084947 6.96583938 H 6.82976606 4.98581493 6.33701158 H 8.73637504 10.78386937 8.75170091 O 10.63907025 5.89976272 5.77405414 H 8.73851245 9.79828933 10.25291768 C 6.79471445 7.11634218 6.88203356 H 5.19727070 5.72760822 6.28264494 H 8.47776248 7.05804167 5.50334682 C 6.27106282 5.90490828 6.07217283 H 6.89759949 7.65223854 9.03646127 H 5.39702752 6.82123247 8.54031849 C 6.49342192 6.86398045 8.37844937 H 6.92801856 5.90427067 8.71452531 H 6.31200725 9.27575511 7.01491244 C 6.07308063 8.39104232 6.39430531 H 6.34092410 8.63032000 5.34429023 H 4.97580503 8.24339137 6.43624422 C 8.52859213 9.77208459 9.16588017 H 7.44087642 9.60639259 9.02925585