Diels-Alder Approach to Biaryls (DAB): Importance of the ortho-nitro Moiety in the [4+2] Cycloaddition.

Size: px

Start display at page:

Download "Diels-Alder Approach to Biaryls (DAB): Importance of the ortho-nitro Moiety in the [4+2] Cycloaddition."

Beryl Lloyd
5 years ago
Views:

1 Supplementary Material for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2008 Diels-Alder Approach to Biaryls (DAB): Importance of the ortho-nitro Moiety in the [4+2] Cycloaddition. Bradley 0. Ashburn and Rich G. Carter* Department of Chemistry, Oregon State University, Cowallis, OR Electronic Supplementary Information: Spectral Data

2 Diels-Alder Approach to Biaryls (DAB): Importance of the ortho-nitro Moiety in the [4+2] Cycloaddition. Table of Contents

3 VI P. S3 N m. : VI. o m P W N t l V I w w w o v N m N ' " W 0 O W m v w - l r IDm. 00,". W N N W X P O 7 m. O W V I ~ N 0419 I P. cl 0 0. P N V I w C m W w o O W g N O O N O V I O l N W W m O x o P w m " x z g r n x x m N N 2 z- -- T-. -.

4 2-nitrophenylacetylene + Me0 diene Current Data Parameters NAME BOA1176 EXPNO 2 PROCNO 1 DU USER /m brada F2 - Acquisition Parameters Date Time INSTRUM DPX4OO PROBHD 5 lrml BBO BB-1H PULPROG Z g ~ g 3 0 TD SOLVENT NS 996 DS 4 SWH - ~~ Hz FIDRES HZ AQ sec RG DW usec 6.OO usec K sec sec DELTA sec TDO 1 P1 PL1 SF MHz CPDPRG2 NUC2 PCPD2 PL2 PL12 PL13 SF02 waltz16 1H usec db db db MHz F2 - Processing parameters SI SF MHz WDW EM SSB 0 LB 3.00 Hz GB 0 PC 1.40 S4

5 2-nitrophenylacetylene + 2-TMSO diene Current Data Parameters NAME BOA1 170 EXPNO 1 PROCNO DU USER F2 - A c a lisition Parameters Date- Time INSTRUM PROBHD PULPROG TD SOLVENT FIDRES TE Dl TDO 1 /m brada DPX4OO 5 mm BBO BB-1H zg CDC Hz Hz sec usec 6.OO usec K sec CHANNEL fl I==='== NUC 1 P1 PL1 SF usg 0.00 db MHz F2 - Processing parameters SI SF MHz WDW no SSB 0 LB 0.00 Hz GB 0 PC 1.00 S5

6 P 0 "r r f, P P W P W W N m-2-2-2vl " O.... N I I O P P P O P W,I o o o o o x m 11 ZgigigiE i! N 0 I1 n II GIIIIIIIXCC a x x P m m m m N N n n n e m n 111 n n - S6

7 2-nitrophenylacetylene + MeO/OH diene Current Data Parameters NAME BOA1177 EXPNO 1 PROCNO 1 DU /m USER brada F Z - Acquisition Parameters Date Time INSTRUM PROBHD 5 mm BBO DPX4OO BB-1H PULPROG zg30 TD SOLVENT CDC 13 NS 32 DS 2 S WH Hz FIDRES Hz AQ RG sec 512 DW usec DE 6.00 usec TE K Dl sec TD 0 1 NUCl P1 PL1 SF01 1H use< 0.00 db MHz F2 - Processing parameters SI SF mw SSB LB GB 0 PC Hz S7

8 ~ g E " a E " " " ~ ~ ~ ~ N W u g N W I 1 5EZz5 v -11 g E E E 3 E 2 2 s Z $ Z 5 g G r0rn.n 2 s E Z F Z c u a m z 2 g c E $ $ 5!a g $ Z E : ~ Y ~ a '2 II. I, I1 2 * F 30 : 0 w r 4 alzcszgi! m 0 0 m C. m I L F P. P 3 : s p a P N. O m :i' V I W V I W - C m o o o r ~ o w ~ N W N F C C C W "N W I C O O O N W V I P r n V I m:w8"z% $ " W $"$ m-j-j-jm " m - 4 O O O W m. W N W. F V I D W X V I Z N.. 5 2% N I1 V I.. Fll W ' W - J F W m VI VI19 1 P. r m z ~ E ~ E K tgfw:l E 0 It 0 II 0 0 m I S8

9 2-nitrophenylacetylene + BnO/TMSO diene Current Data Parameters NAME BOA1181 EXPNO 2 PROCNO I DU USER /m brada F2 - Acquisition Parameters Date Time INSTRUM DPX400 PROBHD 5 mm BBO BB-1H PULPROG TD SOLVENT NS DS 2 S WH Hz FIDRES Hz A sec Dl TDO CHANNEL fl =I====== NUCl P1 PL1 SF01 1H usec 0.00 db MHz F2 - Processing parameters SI SF KHz WDW SSB LB GB PC S9

10 2-nitrophenylacetylene + BnO/TMSO diene BnO d m m m -3 0 P... e. P P W O P P P P Current Data Parameters NAME BOA1181 EXPNO 4 PROCNO 1 DU /m USER brada F2 - Acquisition Parameters Date Time INSTRUM PROBHD DPX nun BBO BE-1H PULPROG Z g ~ g 3 0 TD SOLVENT NS 1918 DS 4 S WH Hz FIDRES Hz A sec RE DW usec DE 6.00 usec TE K Dl sec dl sec DELTA sec TDO 1.-- PLl2 PL13 SF usec db MHz,, CHANNEL... f waltz16 1H usec db db MHz F2 - Processing parameters SI SF MHz WDW EM SSB n LB S10

11 Current Data Parameters NAME BOA1178 lill EXPNO 1 PROCNO DU USER b r a ~ i ~ l 1 F2 - Acquisition Parameter Date I Time INSTRUM DPX400 PROBHD 5 m BBO BB-1H PULPROG zg30 TD SOLVENT CDC13 NS 32 DS 2 S WH Hz FIDRES HZ AQ RG sec DW usec CHANNEL fl = = = = = = = r NUC 1 PI PL1 SF01 1H usec 0.00 db MHz F2 - Processing parameters SI SF MHz WDW no SSB 0 LB 0.00 Hz I " " I ' " ' I ' " ' I " " I ' ~ " I " " I " " I " " I ' " ' I - " " 1 " " I " ' ~ ~ ' I " " I " " l ~ ~ " l " ~ ~ l ' ~ ~ ' l ~ ~ " l " ~ ~ l ' ppm S11

12 Current Data Parameters NRME BOA1178 EXPNO 2 PROCNO 1 DU /m USER brada 1! ' F2 - Acquisition Parameters Date Time INSTRUM DPX4OO PROBHD 5 mm BBO BB-1H PULPROG zgpg30 TD SOLVENT NS 1768 DS 4 s WX Hz FIDRES Hz AQ sec, RG Dw usec DE TE 6.00 usec K Dl sec ' dl sec DELTA sec TDO 1 NUCl PI PL1 SF01 13C 7.80 usec -3.OO db MHz CHANNEL f2 ======== CPDPRG2 Z i 2 PLZ PLl2 PL13 SF02 waltz16 1H usec db d B db MHz F2 - processing parameters SI SF MHz WDW EM SSB 0 LB 3.00 Hz S12

13 :I?.05,". g! - my: m. a L s: L :! :: ZL SL 0 : I x l E L A in: A 0: z t 8 L u. u 3 ' S13

14 mlo'd'dlo w r r r o Z O W W N ' d O U l l N W N Z N ' d l l I 0 w W I rn W m u 4 m.. WII w o m w 11 W O O 0 11 p E g ii n I W W. o m N m u m W. W W N O W N N 0 O'd O O O N w w + m m n m a a w w r 4 o o o o w m. ~ N W. rum^ W X P O M ~ o o ~ N o o ~ ~ ~ ~ P N w ~ o ~ x e e a x x ;d m m m v l v l r n ~ ~ n n o m m n V1 o n YI S14

15 3-nitrophenylacetylene + Me0 diene Current Data Parameters NAME BOA1182 EXPNO 2 PROCNO 1 DU /m USER brada F2 - Acquisition Parameters Date Time INSTRUM DPX4OO PROBHD 5 mm BBO BB-1H PULPROG zg30 TD SOLVENT CDCl3 DS S WH FIDRES AQ RG DW DE TE Dl TD Hz Hz sec usec 6.00 usec K sec 1 Nuc 1 PI PL1 SF db MHz F2 - Processing parameters SI SF MHz WDW no SSB 0 LB 0.00 HZ GB 0 PC 1.00 S15

16 x $ s ~ e o g z g ~ ~ a z a ; : ; y z i q o r r ~ v o II u o r r m g I N W N UN-11 C r O 3 I1 P v 0 I1 I, B m Cn z. E r m P. ID w v r N o o r. o m C( C n U 0 mwln W. r i w 1 r n o o o r d o w w N w w r r r r w r N w l r o o o N w w - m w m $! o o o w m. W N W. r u m ~ m x w ~ w w r m r W.. s g? I, I w m r w m WOmQ, I D. P 0 E $ 2 $ E g g 4 / / $5 / / $ b $ " 5 5 $ g g m n II n II - n n B S

17 4-nitrophenylacetylene + Me0 diene,i PROCNO 1 : # 1 Current Data Parameters NAME BOA1181 EXPNO 1 DU USER bra;: I F2 - Acquisition Parameter Date Time 16.33, INSTRLlM DPX300 PROBHD 5 mm QNP 1H/1 PULPROG zg30 TD SOLVENT CDC 13 NS 31 DS 2 S WH Hz FIDRES Hz AQ sec RG 362 DW usec DE 6.OO usec TE K Dl sec TD 0 1 PI PL1 SF usec -3.oo db MHz F2 - Processing parameters SI SF MHz WDW no SSB 0 LB 0.00 Hz S17

18 e P 0 C C C C P W P N m d d d m fl O.... N I, O L P P O P C I x m!! s: I : I 0 10 m W I C m w d U I.. P I m w 1 1 C O O 0!! s p 2 peeeg peg 1 : : : x z 6 :$E m m n VI n II n 11 n n m r( S18

19 S19

20 3-nitrophenylacetylene + 2-TMSO diene Current Data Parameters NAME BOA1188 EXPNO 3 PROCNO 1 DU USER /n brada F2 - Acquisition Parameters Date Time 7.53 PROBHD 5 mn QNP 1H/1 PULPROG ZgP930 TD SOLVENT CDC13 DS 4 S WH Hz FIDRES Hz AQ sec RG DW usec DE 6.00 usec TE K Dl sec dl sec DELTA sec TDO CHANNEL fl ===n==== NUC 1 PI C 8.80 usec db MHz I / CHANNEL f2 CPDPRG2 waltz16 NUC2 1H PCPD usec PL db PL db PL db SF MHz F2 - Processing parameters SI SF MHz wdw SSB LB GB S20

21 A. L o. -. s l I S! E : = g. - E 5 - : a. -l- 0,' in: a. 0: P i r J l. L" 1 0. P i C n. g 1 E! X ' 2! A. in -, A ' 0: 0 ' in: P i 0.. u 3 ' n., m VI VI, " T o " I : 0 " p N r W. o m o a g g s o m. P ZwR K r 2 z * m m. W m. U N N W X V I o W 6 gos$ Z p P. r n o m. om,,, L?,", P. m N m m w r o o o $ r 0 b m m o o 4 r o. o o c l ~ ~ m o o o o o o m g r o o m o ~ O N O O N O ~ ~ N P O & ~ 2O r w~ z O 2 ~ ~ ~ -.- r. S21 VI ;,,, X R - P 0 L L

22 4-nitrophenylacetylene + 2-TMSO diene w P m m c v m w ~n rl rlrl O P r l L n m m Ln rl P w m m ~ q w TJ TJ flflflfl rl rl rl rlrlrlrl 4 Current Data Parameters NAME BOA1179 EXPNO 5 PROCNO 1 DU /m USER brada F2 - Acquisition Parameters Date Time INSTRUM DPX4OO ' PROBHD 5 mm BBO BB-1H I 1 1 PULPROG zgpg3 0 TD SOLVENT NS 1501 DS 4 S WH Hz FIDRES Hz A sec usec 6.00 usec K sec dl sec DELTA sec TD 0 1 NUC 1 PI PL1 SF C 7.80 usec -3.oo db MHz CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCPD usec PL db PL db PL db SF MHz F2 - Processing parameters SI SF m z WDW SSB LB GB S22

23 m g j % { Z! ma : - 0 m. U I. E. a l U I. - 2' K i % I g! Pi 0 w. K { I x l P l 0. -L in A 0: s I s: ' E E B g Z 2 m = I w 2 m u % ; 0 14 E 2 O W Y P 823 o ~ o m m o m - s $ % Ur3UtlL. r m m = 0 0 N N 0 0 (n 0 4 ( n O N m w ( n o w m. m w O W. O W L " P O N O O W O C C u u u m m n 44 n S23

24 x s ~ z s ~ c3 ; z ~ ; g g g : : 3 ~ ~ 9 gffes:gssgg:ssgazgs;z : ; s z g ~ ~ W E I N W N E N V O P P U L 11 I# P 3 s e s ai c, E ~ a 0 i 6. $ V GI N I1 11 : 62 m C.!2 m L E r g g!. w o l s 0 P N c 0 0 P. o m m :a ti m u 0 m w m W. C. m w r P 2 Z m o o o r m o w w C. C P C. W C.N W I P O O O N W - J P m m. m z W g W? z g m m r? m u 4 I- 0.. % O O O w. m. w N W. m Z ) m X W O t i a,, + o a m m o ~ L L L ~ P E ZbLL!: : 8g8%gNE%E S Z 9 L g L 6 $ ' c. m : ;askeg i peg j ;;;YE 8:: ID O O O O O O ~ ; O O O O O Z ~ I P~ O O ~ I I I - o o I - ~ o o m P - ~ w P., m o z o ~ m m &SwN:L' 0 I1 0 I, 0 0 m E O S24

25 S25 0 'A?. YI 111 L. P. L. 9 ; w z g X mm Nos b a o r Z - z 0 0 r w r m 0 O W - N r c O N m m m o C 0 O N W O P o w m. ~ K ~ E E : :? K a z: l P b b s8:k Xb;,! Z w b g E E E F ~ 2 % L g b 2 $ m o o o o o o m p r o o x n r o N o o N o m m N ~ w m o z o r o m E 2 r g

26 " L ~ S K Z ~ E E W E ~ : 2! ~ s ~ ; ; g:eesezsgzgzsggas;zga s z s g Z o o r w I N W N EN'dll % F g Z z g, PI O'dP6 C L L 11 s r n z m z '0 & II E 3 $ 8 $ ' g 3" 3 I, I1 : La m m P u L n - P C - 3 ; L O Y 0 o n O I - r I r O O P b. N L 'd - o m E N"J g z C r & m w m W. C. N 0 U - " 0 O'd 2 1 Z Z Z Z N C R P Z K m s m w u, C W U ) m. W N W. ~ v u x O O V i!2 a 4 > >? c,, ~ ~ y ~ l l $ $ L i! g O O O w. U ) 4 C. W m m m s C -., Z o k o! 2 ~ ~ 8$ Z G K 1 1 E8ZXi, Z Z 8 L 8 Z b 2 Z E C - Z :ZEB:Z% P a p N $ $5 1: W g $ " E $ g E E m L" 0 I1 0 II S26

27 3-nitrophenylacetylene + BnO/OH diene DU USER F2 Date- Im brada!i, 1 - ~cquisitlan ) ~arameke,s Time INSTRUM PROBHD DPX rn BBO BB-1H ' ' 1 PULPROG zg30 TD SOLVENT CDC13 NS 25 FIDRES Hz AQ sec RG Dw usec DE 6.00 usec TE K Dl sec TDO 1 NUC 1 PI PL1 SF01 1H usec 0.00 db MHz F2 - Processing parameters SI SF m w MHz no SSB 0 LB 0.00 Hz GB 0 PC 1.00 S27

28 3-nitrpphenylacetylene + BnO/OH diene m m m ~ d ~ r n m * ~ o m w ~ rw n d F O r n m U l O P W O d O W N d 0.., r - w m r n w m d m m m t - * d d m d m m O ~ ~ ~ ~ N N N No N o N N d d d d d d d d 4 d d d d d d d Current Data Parameters NAME BOA1183 EXPNO 2 PROCNO 1 DU /m USER brada F2 - Acquisition Parameters Date Time INSTRUM DPXIOO PROBKD 5 ran BBO BB-1H PULPROG zgpg30 TD SOLVENT NS 1204 DS 4 S WH Hz FIDRES Hz AQ sec RG DW usec DE 6.00 usec.- Dl sec dl1 DELTA sec TDO 1 NUCl P1 PL1 SF01 CPDPRG2 NUC2 PCPD2 PL2 PL12 PL13 SF02 13C 7.80 usec -3.OO db MHz CHANNEL f2 =======r waltz16 1H usec db db db MHz ~2 - Processing parameters SI SF MHz SSB LB GB S28

29 - :: s; s l r 3 -i i 0. -i % L K I g-i s l z j i P i U I. P i 0. A in: A 0: s: s: u. u 3 ' E E OWM r 0.. Z Y D o o z o m m om,-, N o m 0 Ln 0 4 W P P N m w w o n w V ' O O W m. W v l t l N N p ) V r 4 r ~ O N O O N O ~ ~ N W W ~ O X O ~ O ~ S29

30 4-nitrophenylacetylene + BnO/TMSO diene OIOI P O O P O W L ~ W ~ N N N mco m m m ~ d W m m N ,,.... P W W L n W d O a 2 c o W m r l 03 T-4 m m e e m m m ~ ~ ~ o m m 0 rld rldddddrlrlrld rl rl w e (q m m o P ~ n,... P P W O P P P P Current Data Parameters NAME BOA1172 EXPNO 2 PROCNO 1 DU /m USER brada ~2 - ~cquisition Parameters Date Time INSTRUM PROBHD 5 mm BBO DPX400 BB-1H PULPROG ZgPg30 TD SOLVENT NS 1846 DS 4 S WH Hz FIDRES Hz A sec RG DW usec DE 6.00 usec TE K Dl sec dl1 0 : sec DELTA sec TDO CHANNEL fl =.===r== 1 NUCl P1 PLl SF01 13C M H Z : (III CHANNEL f2 =====r.= I PCPDZ PLZ PLl2 PLl3 SF usec db db db MHz F2 - Processing parameters S SF MXz WDW EM SSB LB S30

31 ~ - phenylacetylene + Me0 diene o ~ ~ ~ ~ N o ~ ~ ~ N w N P ~ ~ ~ w ~ ~ L ~ ~ L ~ O I o w ~ ] ~ w L ~ N w ~ c o L ~ ~ ~ ~ L Current ~ o P Data Parameters ~ ~ ~ ~ ~ ~ ~ ~ P W W ~ ~ ~ ~ ~ O O ~ ~ I C O C O C W O P W W ~ I ~ ~ ~ ~ ~ \ ~ \ P P W L ~ L NAME ~ ~ ~ BOA1192 m m m m v v e e e e e e e e e e e e m m m m m m m m ~ ~ r l ~ ~ ~ ~ ~ ~ ~ ~ o EXPNO 1 P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P m PROCNO DU /m USER brada I F2 - acquisition Parameters Date Time INSTRUM DPX4OO PROBHD 5 mn BBO BB-1H PULPROG zg30 TD SOLVENT CDC13 NS 19 DS 2 S WH Hz FIDRES HZ AQ sec RG DW usec DE TE 6.OO usec K Dl sec TD CHANNEL fl ======== NUCl 1H P usec PL db SF MHz i ljl F2 - Processing parameters SI SF MHz WDW no I SSB LB GB PC S31

32 m "7 z. u L VI LU " t.. P F O O C *. z o m N " 7 w m W. " N U O W C C I - c w W N W I w O O O N w m c m m m a m ~ r d w ts E! w m. W N W N II "7.. W I I o o o w. -41-WO, P W Q I P. E % g o s, ~ p ~ ~ - g g 2 j 8 1 & g z P P Y ~%~~~~~ g),,;$ I, I, rt n II n 18 n n - 8 VI S32

33 :'9 c n. I P i c n. I 2-1 =in: a. s : 2 : 0 m : W h -. = % I % L Z! P ' in: S! 3.08=. s j z I :! : j 2 in: 2-0. P i ul. 8 L 7J 7 J. 3 ' P n N P F m 0 0. o. 4b P I1 II C O O X!I N N 0 VI 0 4 V I O N m VI 0 - m OVlVl 0. O O C P C O N O O N O 0 m. P F 1 0F 0 0 u VI. m u O N V I F P m m u m w P P S33

34 w o r m ornrnm3::2 m 4 1 w 8 m ' C. 0 lli 3 '" m u N W M L ' W '"N ozogg:; g p p p X z 0 " ON PW WN N WE 0 N: W II\ I z ~... 0 ' " W0 UP I? O K W. P ' \ O O W N O O O N w w l r m ' " m. \ O N -. r w. W Y I ' W r n ' m m P ~ P 0 0 ' N O O N P - J ~ P W V I V I r n X C C m m m m lorn :$2 n n n m m n S34

Preparation of endohedral fullerene containing lithium 60 ) and isolation as pure hexafluorophosphate salt ([Li 60 ][PF 6 ])

This journal is The Royal Society of Chemistry 212 Supplementary Information Preparation of endohedral fullerene containing lithium (Li@C ) and isolation as pure hexafluorophosphate salt ([Li + @C ][PF