Development of an Enantioselective Route towards the. Lycopodium Alkaloids: Total Synthesis of Lycopodine.

Transcription

1 Development of an Enantioselective Route towards the Lycopodium Alkaloids: Total Synthesis of Lycopodine. Hua Yang and Rich G. Carter* Department of Chemistry, Oregon State University, Corvallis, OR Electronic Supplementary Information: NMR Spectra S1

2 Development of an Enantioselective Route towards the Lycopodium Alkaloids: Total Synthesis of Lycopodine. Table of Contents Compound Page # Number 18 S3 21 S5 24 S7 33 S9 35 S11 31 S13 25 S15 36 S17 37 S19 60 S21 38b S23 39b S25 62 S27 63 S29 38c S31 39c S33 65 S35 38d S37 39d S39 67 S41 38e S43 39e S45 41 S47 42 S49 44 S51 8 S53 7a S55 6 S57 49 S59 5 S61 51 S63 1 S65* * Includes comparison with authentic sample and comparison to literature values. S2

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9 ..,.r' I, I ( I I I I I I I I I I I I I ppm S9 _J F2 - Processing parameters SI SF MHz WOW EM I I I I I I I I I SSB o LB 0.70 Hz ppm ppm GB o PC CHANNEL fl NUCI IH PI usee PLIO.00 db SFOI MHz sec TOO I o DW usee 14 DE 6.00 usee TE K H2N-#-Q-(CH2)1fCH3 AQ sec RG 128 o F2 - Acquisition Parameters Oate_ Time INSTRUM OPX400 PROEHD 5 rom BBO BB-IH PULPROG zg 30 TO SOLVENT COC13 NS 32 OS 2 SWH Hz FIORES Hz \I USER yang r--r- r-r-r---r-- ljl NNNNrlrlrlrlrlrlrlrlrlOOOOOOO PROCNO OU 1 In COCO MMMN o EXPNO 2 00 CO\.D r---r---fir--- -=:f'lnooo 0') 0') Current Data Parameters NAME HYsu1fonarnide

10 Current Data Parameters NAME HYsulfonamide EXPNO 3...r OOMOOt.f)1...D N <::j( 0:::1 r- Lf) '<;j' \D'<l'N PROCNO MOr- DU In m COOOr-1...D1...D USER yang ("") NNNNN r-r-\d M rlrlrlrlm r-r-r- 1 \1/ PROBHD F2 - Acquisition Parameters Date Time INSTRUM DPX400 5 mrn BBO BB-IH PULPROG zgpg30 TD SOLVENT NS 253 DS 4 SWH Hz FlORES Hz AQ sec RG DW usec DE 6.00 usec TE K (CH2)11-GH D sec 3 dll sec o DELTA sec 14 TDO 1 CHANNEL f1 ======== NUC1 13C PI 7.80 usee PL db SF MHz ppm CHANNEL f2 ======== CPDPRG2 wa1tz16 NUC2 1H PCPD usec PL db PL db PL db SF MHz F2 - Processing parameters S SF MHz WOW EM SSB 0 LB 3.00 Hz GB 0 PC d. I PII" lj.. 1"',l., "'",II.lil..,. oi.ji..,,.,. I I I I I I I I I I I I I I I r I I I Tnrr I I I ppm S10

11 I I I I I I I I I [ I I t I I I I I I I 1 '.. I., r '-r-' T ppm 1 ( S11 I I 7.5 ppm ppm I '"-'-l ',,, I ',,, I ',,, I ', J F2 - Processing parameters SI SF MHz WOW EM SSB o LB.70 Hz GB o PC.00 CHANNEL fl =======, NUC1 1H I N-S II PI usee Cbz H' 0 PL10.00 db SF MHz 16 TDO 1 TE K D sec DW usee DE 6.00 usee DS 2 SWH Hz FIDRES Hz AQ sec RG 512 I o M r- f'r---r---r-e- \'\'If U") '" M NNN0J...-Irlrlrl...-lrlOOOOOOooo I INSTRUM PROBHD PULPROG TD SOLVENT NS 5 rom DPX400 BBO BB-IH zg CDC13 32 N '" M...-l -..::r...-inooo\o O'l '<;j'lmmnn N M Time U") M M '" N F2 - Acquisition Parameters Date_ Current Data Parameters NAME HYCbzHuaCat EXPNO 2 PROCNO 1 DU In USER yang

12 0 e- CO M 0000 ['-M['-o;;;21N ['-Wo:;jl'<;jlN...-ll.Jl e- l!100cooocoooren C"1NNNNNN CO '" \v.--i.--i r-lr-lrlr-lrlr-lrl NNOOOr-lNffiOOOr-l\..DMNOOr-Wl.JlMrlWl.Jlr-lMMWl.JlOOW Current Data Parameters NAME HYCbzHuaCat EXPNO PROCNO DU 3 1 In USER yang F2 - Acquisition Parameters Date Time INSTRUM DPX400 PROBHD 5 rom BBO BB-IH PULPROG zgpg30 TD SOLVENT NS 4999 DS 4 SWH Hz FIDRES Hz AQ sec RG DW usee DE 6.00 usee TE K 1\.0 r:;?-q-( 2l11 CH 3 D sec II CH dll sec Cbz H' 8 DELTA sec TDO 1 16 CHANNEL fl "====="= NOC1 l3c Pi 7.80 usee PL1-3,00 db SF01 100, MHz u CHANNEL f2 ======== CPDPRG2 waltz16 NOC2 1H PCPD usee PL db PL db PL13 17,40 db SF MHz F2 - processing parameters 5I F MHz,,,,,,,,, I,,,,,, wnw EM '" I"" I"" I"" I" ' I"" I"" I"" B 0 LB 3.00 Hz 128 ppm ppm GB 0 PC 1.40 I I I I I I I I I,n I I I I I I "1""'''''I''''''''''''''"''''""n''''lmn'''Tnmn ppm S12

13 S13 I I I I I I I I'. I ".. T.. 1 'I I I'.. I.,. -r,-,n.... I ppm I ',,,I' 'I 8.5 ppm 7.5 ppm 4.0 ppm GB 0 PC Processing SI SF MHz WDW EH, I, " I '" I ',, SSB 0 LB 0.30 H:: ) l F2 CHANNEL f1 ::::::0;:::::::: NUC1 1H PI usee PL db SFOl MHz sec TOO 'f'j/"'( "-o-(ch )1f CH 3 OW usee H I N-S II // 2 DE 6.00 usee H 0 TE K 1\ 0 - RG FIDRES Hz 0 AQ sec SOLVENT edc13 NS 32 OS 2 SWH Hz \\ $; F2 - Acquisition Parameters Date Time INSTRUM OPX300 PROBHD 5 min QNP 1Hl1 PULPROG zg30 TO r-- O'>O'>N '!) '!) OJ Current Data Parameters NAME HY7-30 '" r-- "'U"l'" o OJ OJ "''''0 NNN EXPNO 1 PROCNO 1 OJ OJr--r-- r--r--r-- DU In USER yang

14 c Current Data Parameters NAME HYHuaCat EXPNO 5 0 rl ffirlrlr'llil CO PROCNO 1 "" r-- NNNNN rl rl rl.-lrl..-l.-l OU In 0 r-r--r-i.di..d USER yang I F2 - Acquisition Parameters Date Time lnstrum OPX400 PROBHD 5 rom BBO BB-1H PULPROG zgpg30 TO SOLVENT COC13 NS OS 4 SWH Hz FlORES Hz AQ sec RG DW usee 0 DE 6.00 usee 1\ 0 - TE K "-O-(CH )1f CH sec H I N-S 8 II 2 d sec H 0 DELTA sec 11 TOO 1 CHANNEL fl ======== NUC1 13C PI 7.80 usee PL db SF MHz CHANNEL f2 ======== CPDPRG2 waltz16 NUC2 1H PCP usee PL db PL db PL db SF MHz ppm F2 - Processing parameters Sl SF MHz WOW EM SSB o LB 3.00 Hz GB o PC "'''''''1 I "urn I I I I I I I ", '1 I I UTlT I I I I I I..,,,,, ppm S14

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68 Comparison of 13 C NMR Data for Synthesis and Natural Lycopodine (1) Synthetic 1 13 C NMR Data (CDCl 3, 100 MHz) Natural 1 13 C NMR Data a (CDCl 3, Jeol FX 90Q Spectrometer) a Kraus, G. A.; Hon, Y. S. Heterocycles 1987, 25, S68