Supplementary Information. Homoallylglycine residues are superior precursors to orthogonally modified thioether containing polypeptides
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- Robyn Blanche Harrell
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1 Etroni Suppmntry Mtri (ESI) or CmComm. Tis journ is T Roy Soity o Cmistry 2018 Suppmntry Inormtion Homoyyin rsius r suprior prursors to ortoony moii tiotr ontinin poypptis Ps Prin, Eri G. Grknin n Timoty J. Dmin * Mtris n mtos Unss spii, post-poymriztion moiition mistry ws prorm in ss vis unr mint tmospr. Tio-n rtions wr prorm in 1 rm srw top ss vis pp wit spt to ow sprin. An Exo Trr Rpti-Go 5.0 ompt uorsnt tropi trrrium mp ws us s t utrviot it sour. Sm mou mistry ws prorm in t-ri sswr unr nitron tmospr, unss otrwis spii. THF n xns wr ss wit initron n pss trou n umin oumn or us. A otr rnts n sovnts wr us s riv. Unss otrwis spii, rtions wr prorm t mint tmprtur (. 20 C). In-ous ioniz wtr ws us or quous mistry n iysis unss otrwis spii. Cirur iroism (CD) sptrosopy ws prorm on smps prpr usin ioniz wtr itr trou Miipor Mii-Q Bio A10 itr systm unss otrwis spii. CD sptr wr ot usin 0.1 or 0.5 m/ml soutions o poyppti on n Ois DSM 10 sptropotomtr usin 0.1 m pt nt qurtz uvtt. Prnt α-i ontnt o poypptis ws stimt usin t ormu % α- ix = 100 ( [θ] )/39000), wr [θ] 222 is t msur mor iptiity t 222 nm. Tinyr romtorpy ws prorm wit EMD 60 F254 pts (0.25 mm tiknss) n spots wr visuiz usin UV mp or KMnO 4 stin. Siiy Siis G60 sii ( µm) ws us or oumn romtorpy. Sii us or romtorpi puriition o NCA monomrs ws ri unr vuum t 250 C or 48 ours n tn stor in initron i ovox. Compositions o moi pss us or romtorpy n ompositions o sovnt systms us or irur iroism r ivn in voum prnts. Diysis ws prorm wit rnrt uos tuin otin rom Sptrum s. NMR sptr wr ror on Brukr AV400 instrumnt wit mi sits rport rtiv to t utrt sovnt us. Inrr sptr o soution smps wr ot usin Prkin Emr 1605 FT-IR Sptropotomtr. Soi stt FTIR sptr wr ot usin Prkin Emr Sptrum On FT-IR Sptropotomtr wit Prkin Emr Univrs ATR Smpin Assory. DART-MS sptr wr ot on Trmo Extiv Pus MSD (Trmo Sintii) quipp wit n ID-CUBE ion sour t t ow sorption sttin n Vpur Intr (IonSns). Bot t sour n MSD wr ontro y Exiur v Anyts wr issov 1 m/ml in 1:3 THF:MCN n S1
2 spott onto OpnSpot smpin rs (IonSns). Ioniztion ws ompis usin H psm wit no ition ioniztion nts. Mss irtion ws rri out usin Pir LTQ Vos ESI (+) n (-) Ion irtion soutions (Trmo Fisr Sintii). Tnm prmtion romtorpy/it sttrin (GPC/LS) ws prorm t 25 o C usin n SSI Auow Sris III pump quipp wit Wytt DAWN EOS it sttrin n Opti REX rrtiv inx ttors. Sprtions wr iv usin 100 Å n 1000 Å PSS-PFG 7 µm oumns t 30 ºC wit 0.5% (w/w) KTFA in 1,1,1,3,3,3- xuoroisopropno (HFIP) s unt n smp onntrtions o 10 m/m. Enntiomri xss o L-H ws msur inst rmi stnr usin n Aint 1260 Ininity HPLC. Sprtions wr iv usin Cirpk AD-H 5 µm oumn wit 10% isopropno in xns s unt n smp onntrtions o 1 m/m. Mtin points wr msur usin DiiMt MPA160 SRS mtin point pprtus wit rmp rt o 5 o C/minut. Arvitions: N-roxynyri (NCA), r o poymriztion (DP), L-mtionin (Mt), poy(lmtionin) (M), ( L-omoyyin (H), poy(l-omoyyin) (G HA ), DL-omoyyin (r-h), poy(dl-omoyyin) ((r-g HA )), 2,2-imtoxy-2-pnytopnon (DMPA), α- mtoxy-ω-isoynoty-poy(tyn yo) (PEG-NCO), monomr to inititor rtio (M:I), isprsity (M w /M n or Ð), mty ioi (MI), utrviot it irrition (ν), mour wit uto (MWCO), ioniz (DI), room tmprtur (RT), quivnts (q), isopropy oo (IPA), tonitri (MCN), ttryrourn (THF), mtno (MOH), ty tt (EtOA), i ti i (AOH), ormi i (HCOOH), (+/-) mporsuoni i (CSA), ity tr (Et 2 O), ioromtn (DCM), potssium trt-utoxi (KOtBu), trt-uty yroproxi (TBHP), N,N-Dimtyormmi (DMF), 2-[2-(2- mtoxytoxy)toxy]tntio (meg 3 SH), 2-[2-[2-(2-mtoxytoxy)toxy]toxy]tntio (meg 4 SH), 1-mrpto-11-yroxy-3,6,9-trioxunn (EG 4 SH), meg 3 SH moii poy(lomoyyin) (meg 3 -G HA ), meg 4 SH moii poy(l-omoyyin) (meg 4 -G HA ), EG 4 SH moii poy(l-omoyyin) (EG 4 -G HA ), meg 4 SH moii poy(dl-omoyyin) (meg 4 - (r-g HA )), 1-tio-β-D-uopyrnos ttrtt moii poy(l-omoyyin) (G(OA) 4 -G HA ), 1-tio-β-D-uopyrnos moii poy(l-omoyyin) (G-G HA ), rotry vportion (rotovp), ro (r), out (), out o outs (), out o out o qurtts (q), out o qurtts (q), out o tripts (t), mutipt (m), pntt (pnt), qurtt (q), sint (s), tript (t), Dirt Anysis in R Tim Mss Sptromtry (DART-MS). S2
3 1. Syntsis o mino is n NCA monomrs Sm S1. Syntsis o omoyyin mino is. (A) r-h NCA (B) H NCA. N-(Dipnymtyn)-DL-omoyyin trt-uty str. Tis ompoun ws syntsiz y oowin prviousy rport mto. 1 A 10% THF soution o potssium trt-utoxi (1.9, 17 mmo) ws ropwis to 10% THF soution o N-(ipnymtyn)-yin trt-uty str (2.5, 8.5 mmo) t -70 C (EtOA/iqui nitron t). Atr 15 minuts, 2.0 ml (20 mmo) 3-utny romi ws vi syrin. T rtion ws t wrm to mint tmprtur tn trnsrr to 30 C wtr t n t stir ovrnit. T rtion ws tn t oo to mint tmprtur n qun wit 30 ml o sturt mmonium ori soution. T rsutin yrs wr prtition in sprtory unn, n t quous yr ws tn xtrt wit 4 x 25 ml DCM. Comin orni xtrts wr ws wit rin, ri wit nyrous soium sut, n votis wr rmov unr ru prssur. T rsutin oi ws purii y sii romtorpy wit 8 % EtOA in xns s moi ps. Sovnt ws rmov unr ru prssur to yi t prout s p yow oi (2.8, 93% yi). 1 H NMR (400 MHz, CDC 3, 25 C): δ (r m, 2H), (r m, 6H), (r m, 2H), (q, J = 27.2, 6.1 Hz, 1H), (r m, 2H), 3.93, (t, J = 6.2 Hz, 1H) (r m, 4H), 1.44 (s, 9H). S3
4 DL-Homoyyin yroori, r-h. Tis ompoun ws syntsiz y oowin prviousy rport mto. 1 N-(Dipnymtyn)-DL-omoyyin trt-uty str (1.72 ) ws suspn in 27.5 ml o 2 M quous HC, n stirr rpiy t mint tmprtur or 3 ours. T suspnsion m r soution in 60 minuts n yow oi n to sprt. Orni yprouts wr rmov y wsin t rtion mixtur wit 3 x 20 ml DCM. T quous yr ws tn onntrt unr ru prssur n urtr onntrt unr i vuum to iv t prout s wit soi (654 m, 85 % yi). 1 H NMR (400 MHz, D 2 O, 25 C): δ (r m, 1H), (q, J = 17.2, 1.6 Hz, 1H) (, J = 11.8, 8.8 Hz, 1H), 3.87 (t, J = 12.5 Hz, 1H), (q, J = 7.0 Hz, 2H), (r m, 2H). Sptr t wr onsistnt wit prviousy puis rsuts. 1 Dity 2-omoy-2-tmiomont. Tis ompoun ws syntsiz y oowin prviousy rport mto. 2 A soution o ity 2-tmiomont (45, 210 mmo, 1.0 q) in DMF (300 ml) ws prpr in roun ottom sk n pp wit sptum. Sprty, suspnsion o 60 % NH (9.1, 230 mmo, 1.1 q) in DMF (100 ml) ws prpr in Snk sk n stirr in n mint tmprtur wtr t unr N 2 tmospr. T mont soution ws sowy nnu trnsrr into t NH suspnsion (ution: xotrmi). T rsutin mixtur ws stirr 10 min. 3-Butny romi (23 ml, 230 mmo, 1.1 q) ws tn in on portion vi syrin. T mixtur ws stirr or 16 on 60 C oi t, n tn qun wit AOH (2 ml) n onntrt y rotry vportion, tn usin i vuum. T rsiu ws issov in Et 2 O (250 ml) n ws wit H 2 O (2 x 200 ml), n tn t orni ps ws ri ovr MSO 4 n onntrt y rotry vportion. Tis ru mtri ws purii y oumn romtorpy (25-35% EtOA/xns) to provi ity 2- omoy-2-tmiomont s p yow soi (43, 76 % yi). R F = 0.32; 25% EtOA/xns. 1 H NMR (400 MHz, CDC 3, 25 C): δ 6.79 (s, 1 H), 5.75 (q, J = 17.1, 10.3, 6.5 Hz, 1 H), 5.03 (q, J = 17.1, 1.7 Hz, 1 H), 4.97 (q, J = 10.2, 1.5 Hz, 1 H), 4.25 (q, J = 7.1 Hz, 4 H), 2.45 (m, 2 H), 2.04 (s, 3 H), 1.92 (m, 2 H), 1.25 (t, J = 7.0, 6 H). S4
5 N-ty-DL-omoyyin. Tis ompoun ws syntsiz y oowin prviousy rport mto. 2 Dity 2-omoy-2-tmiomont (13, 49 mmo) ws suspn in quous 1 N KOH (2.6 q). T mixtur ws rux wit viorous stirrin. T initiy ipsi mixtur m omonous tr. 30 min. Htin ws mintin or 3 in tot. T mixtur ws just to ph 3.5 (tmprtur ompnst) wit on. HC. T mixtur ws tn rux or n ition 1. T ph ws tn just in k to ph 3.5 usin on. HC (Not: t ph riss s t roxytion prorsss). T mixtur ws in rux or n ition 2 tn ow to oo to mint tmprtur. T soution ws tn onntrt to out 2/3 its oriin voum y rotry vportion. T rsutnt mr mixtur ws trt wit tivt ro (12 ml o powr). Atr stirrin or 10 min, t suspnsion ws itr. T oorss itrt ws just to ph 2.0 wit on. HC. Tis mixtur ws tn xtrt wit 4 x 80 ml o EtOA. T orni xtrts wr ri ovr N 2 SO 4 n onntrt y rotry vportion to provi N-ty-DL-omoyyin (7.7, 96 % yi) s oorss soi. 1 H NMR (400 MHz, D 2 O, 25 C): δ 5.89 (q, J = 17.2, 10.3, 6.8 Hz, 1 H), 5.12 (q, J = 17.2, 1.7 Hz, 1 H), 5.06 (m, 1 H), 4.35 (, J = 9.5, 4.7 Hz, 1 H), 2.21 (m, 2 H), 2.06 (s, 3 H), 2.01 (m, 1 H), 1.86 (m, 1 H). L-Homoyyin. Tis ompoun ws syntsiz y oowin prviousy rport mto. 2 A 300 mm quous soution o N-ty-DL-omoyyin (46, 290 mmo) ontinin 5 mm KH 2 PO 4 ws prpr in Snk sk. T soution ws just to ph wit quous 4 N KOH. T mixtur ws p in 40 C oi t n ss y stirrin unr N 2 or 15 min. Porin mino ys (4.2 U pr mmo o N-ty-DL-omoyyin) ws n t rtion mixtur ws nty stirr. At st tim points 50 µl iquots wr rmov n nyz usin ninyrin ooromtri ssy. 2 T ph o t soution ws prioiy msur n i nssry rjust to ph y ition o 4 N KOH. Wn t ninyrin ssy sow no urtr inrs in mino i onntrtion, t rsoution rtion ws trmint y riy tin t mixtur to 60 o C oow y stirrin wit tivt ro (72.5 ml o powr). T mixtur ws vuum itr to yi oorss itrt, wi ws just to ph 1.5 wit on. HC, n tn ws wit EtOA (3 x 490 S5
6 ml). T quous ps ws ppi onto Dowx 50WX8 oumn (490 ml) n st y usin t oumn wit H 2 O unti t unt r nutr ph oow y sorption o t mino i y utin wit quous 1.0 N NH 3. L-Homoyyin ws rovr s oorss soi tr rotry vportion oow y yopiiztion (15.3, 92 % yi s on mount o N-ty-Lomoyyin). 1 H NMR (400 MHz, 0.5 % TFA-/D 2 O, 25 C): δ 5.80 (m, 1 H), 5.09 (m, 1 H), 5.02 (m, 1 H), 4.02 (m, 1 H), 2.15 (m, 2 H), 2.0 (m, 2 H). [α] 24 D = ( 1.00, 1 N HC). Sptr t wr onsistnt wit prviousy puis rsuts. 2 N-(Cronzyoxy)-DL-omoyyin. DL-Homoyyin yroori (104 m, 0.64 mmo) ws issov in DI wtr (9.0 ml). Soium iront (586 m, 7.0 mmo) ws to t rsutin soution n t rtion mixtur ws t stir t room tmprtur or 10 minuts. T rtion ws tn oo to 0 C n nzy oroormt (144 m, 0.84 mmo) ws ropwis. T rtion ws t wrm to room tmprtur ovrnit wit viorous stirrin. T rtion mixtur ws trnsrr to sprtory unn n ws wit 4 x 6 ml Et 2 O. T quous yr ws tn rout to ph 2 wit 3M HC n xtrt wit 4 x 5 ml EtOA. T EtOA xtrts wr ri wit N 2 SO 4, nt, onntrt unr ru prssur n urtr onntrt unr vuum to iv wit soi (79.4 m, 48 % yi). 1 H NMR (400 MHz, CDC 3, 25 C): δ (r m, 5H), (r m, 1H), (r m, 5H), (r m, 1H), (q, J = 7.1 Hz, 2H), (r m, 2H). 13 C NMR (100 MHz, CDC 3, 25 C): δ 177.3, 156.1, 136.6, 136.1, 128.6, 128.3, 128.2, 116.1, 67.2, 53.3, 31.5, MP = C. N-(Cronzyoxy)-L-omoyyin. L-Homoyyin (58 m, 0.46 mmo) ws issov in 1M soium iront (5 ml) n t stir or 10 minuts. T rtion ws tn oo to 0 C n nzy oroormt (108 m, 0.63 mmo) ws ropwis. T rtion ws t wrm to room tmprtur ovrnit wit viorous stirrin. T rtion mixtur ws trnsrr to sprtory unn n ws wit 4 x 3 ml Et 2 O. T quous yr ws tn rout to ph 2 wit 3M HC n xtrt S6
7 wit 4 x 2 ml EtOA. T EtOA xtrts wr ri wit N 2 SO 4, nt, onntrt unr ru prssur n urtr onntrt unr vuum to iv wit soi (90 m, 75 % yi). 1 H NMR (400 MHz, CDC 3, 25 C): δ (r m, 5H), (r m, 1H), (r m, 5H), (r m, 1H), (q, J = 7.1 Hz, 2H), (r m, 2H). 13 C NMR (100 MHz, CDC 3, 25 C): δ 177.3, 156.1, 136.6, 136.1, 128.6, 128.3, 128.2, 116.1, 67.2, 53.3, 31.6, MP = C. Fiur S1. Cir HPLC romtorm o N-(ronzyoxy)-DL-omoyyin. Fiur S2. Cir HPLC romtorm o N-(ronzyoxy)-L-omoyyin. Amino i N-roxynyri (NCA) monomr syntss. NCA monomrs wr prpr usin prviousy stis mto. 3 Cution! Posn is xtrmy zrous n mniputions must prorm in w-vntit mi um oo wit propr prson prottion n nssry S7
8 prutions tkn to voi xposur. Atr vportion o ru rtion mixturs to rynss usin Snk mnio, ru prouts, in s Snk sks unr vuum, wr rout into initron i ovox or puriition. T mto o puriition vri or monomr, s ti ow. L-Mtionin N-roxynyri, Mt NCA. Purii vi oumn romtorpy usin 33 % THF in xns. Sptr t wr onsistnt wit prviousy puis rsuts. 3 DL-Homoyyin N-roxynyri, r-h NCA. Purii vi oumn romtorpy usin 33 % THF in xns. DL-Homoyyin yroori (590 m) ws us to prpr r-h NCA, wi ws otin s oorss soi (408 m, 73 % yi). 1 H NMR (400 MHz, CDC 3, 25 C): δ 6.40 (s, 1H), (r m, 1H), (m, 2H), (m, 1H), (q, J = 6.9 Hz, 2H), (m, 1H), 1.93 (pnt, J = 7.1 Hz, 1H). 13 C NMR (100 MHz, CDC 3, 25 C): δ 169.7, 153.0, 135.6, 117.3, 57.1, 30.8, DART-MS m/z = [M H] - ( or C 7 H 8 O 3 N: ). MP = C. % Trnsmittn Wvnumr (m -1 ) S8
9 5 RI x 10 4 (RIU) Tim (Min) Fiur S3. TOP: FTIR sptrum o r-h NCA (50 m/ml in THF). Not NCA ns t 1856 n 1790 m -1, n kn strt t 1642 m -1. BOTTOM: SEC Cromtorm o r-h NCA in 0.5% (w/w) KTFA in HFIP. RIU = ritrry rrtiv inx units. L-Homoyyin N-roxynyri, H NCA. Purii vi oumn romtorpy usin 33 % THF in xns, oow y 2x rrystiztion rom THF/xns t -35 C. L-Homoyyin (460 m) ws us to prpr H NCA, wi ws otin s wit soi (370 m, 66 % yi). 1 H NMR (400 MHz, CDC 3, 25 C): δ 6.51 (s, 1H), (r m, 1H), (m, 2H), (r m, 1H), (r m, 2H), (m, 1H), 1.93 (pnt, J = 7.2 Hz, 1H). 13 C NMR (100 MHz, CDC 3, 25 C): δ 169.7, 153.0, 135.5, 117.4, 57.1, 30.8, 29.2 DART-MS m/z = [M H] - ( or C 7 H 8 O 3 N: ). MP = C. % Trnsmittn Wvnumr (m -1 ) S9
10 5 RI x 10 4 (RIU) Fiur S4. TOP: FTIR sptrum o H NCA (50 m/ml in THF). Not NCA ns t 1856 n 1790 m -1, n kn strt t 1642 m -1. BOTTOM: SEC romtorm o H NCA in 0.5% (w/w) KTFA in HFIP. RIU = ritrry rrtiv inx units. 2. Homopoymriztions o H n r-h NCAs Gnr Prour or Poymriztion o H NCA. A poymriztion rtions wr prorm in initron i ov ox usin nyrous sovnts. To soution o H NCA in THF (164 m, 1.05 mmo, 25 m/ml) ws soution o Co(PM 3 ) 4 in THF (970 µl, 52.5 µmo). On mix, t rtion ws t stn t mint tmprtur or 1-2, n omption o poymriztion ws onirm y FTIR. Poymriztion t irnt monomr to inititor rtios us wr oun to ompt witin 2. T ompt rtion ws rmov rom t ov ox n 1-2 rops o 3 M HC wr. T poymr ws tn pripitt wit DI wtr, ntriu t 3000 rpm, n t suprntnt ws isr. T pt ws ws 3 tims wit DI wtr n tn yopiiz to yi poy(lomoyyin), G HA, s wit soi (105 m, 95 % yi). 1 H NMR (400 MHz, TFA-, 25 C): δ (q, J = 17.7, 14.2 Hz, 1H), (r m, 2H), (, J = 8.4, 7.0 Hz, 1H), (r m, 2H), (r m, 2H) Tim (Min) M:I M n ( 1 H NMR) DP ( 1 H NMR) M w /M n Yi (%) N/A N/A N/A N/A 90 T S1. Syntsis o G HA t irnt monomr to inititor rtios (M:I) usin Co(PM 3 ) 4 inititor in THF t 20 C. DP = numr vr r o poymriztion trmin or PEG-NCO n-pp ins usin 1 H NMR intrtions. Yi is t tot isot yi o purii poyppti. N/A = not trmin u to insouiity o G HA in 0.5% (w/w) KTFA in HFIP. S10
11 Gnr prour or poymriztion o r-h NCA. A poymriztion rtions wr prorm in initron i ov ox usin nyrous sovnts. To soution o r-h NCA in THF (173 m, 1.11 mmo, 25 m/ml) ws soution o Co(PM 3 ) 4 in THF (1.00 ml, 55.0 µmo). On mix, t rtion ws t stn t mint tmprtur or 2, n omption o poymriztion ws onirm y FTIR. Ony poymriztions wit M:I rtios up to 20:1 wr oun to o to omption witin 2 ours, poymriztions t ir M:I rtios i not o to omption vn tr mny ours. Atr 2 ours, t rtion ws rmov rom t ov ox n 1-2 rops o 3 M HC wr. T poymr ws tn pripitt wit DI wtr, ntriu t 3000 rpm, n t suprntnt ws isr. T pt ws ws 3 tims wit DI wtr n tn yopiiz to yi poy(dl-omoyyin), (r-g HA ), s wit soi (100 m, 85 % yi). 1 H NMR (400 MHz, TFA-, 25 C): δ (r m, 1H), (r m, 2H), 4.74 (r s, 1H), (r m, 2H), (r m, 2H). M:I Monomr DP M w /M n Yi (%) Convrsion 20 Compt Inompt N/A N/A Inompt N/A N/A Inompt N/A N/A 63 T S2. Syntsis o (r-g HA ) t irnt monomr to inititor rtios (M:I) usin Co(PM 3 ) 4 inititor in THF t 20 C. DP = numr vr r o poymriztion. Yi is t tot isot yi o purii poyppti. N/A = Not trmin u to inompt poymriztion rtion. 8 DRI x 10 5 (RIU) Fiur S5. GPC Cromtorm o (r-g HA ) 43 in 0.5% (w/w) KTFA in HFIP. RIU = ritrry rrtiv inx units Tim (Min) S11
12 % Trnsmittn m m Wvnumr (m -1 ) Fiur S6. Soi stt FTIR o (r-g HA ) 43. T Ami I n Ami II ns t 1626 n 1529 m -1, rsptivy, r rtristi o β-st onormtion. Gnr prour or nppin o poypptis wit PEG ins. T nr prour or poymriztion o H NCA ws oow. On t rtion ws trmin to ompt y FTIR, soution o α-mtoxy-ω-isoynoty-poy(tyn yo), PEG-NCO (MW = 1000 D, 4 q pr Co(PM 3 ) 4 ) in THF ws to t poymriztion mixtur insi initron i ovox. T rtion ws t stn ovrnit, n tn rmov rom t ovox. 1-2 rops o 3M HC wr tn n t rtion ws pripitt wit wtr, ntriu t 3000 rpm n t suprntnt ws isr. T pt ws ws 3 tims wit DI wtr to rmov unonjut PEG-NCO, n t rsutin pt ws tn yopiiz to yi PEG-npp poyppti s wit soi. To trmin t mour wit o t poypptis (M n ), 1 H NMR sptr wr otin in utrt triuoroti i (TFA-) or utrt oroorm (CDC 3 ) ontinin 1-2 rops o TFA-. Simir to prours sri in itrtur, 4 t intr o t kn proton rsonn o G HA t ppm ws ompr to t intr o t poytyn yo rsonn t δ 4.01 (TFA-) or δ 3.64 (CDC 3 / TFA-) to otin G HA nts (s sptr t stion). 3. Tio-n moiition o G HA n (r-g HA ) omopoypptis Sm S2. Syntsis o oiotyn yo tios. S12
13 p-tounsuony trityn yo mty tr. Tis ompoun ws syntsiz usin prviousy rport prour.5 H2O (10.0 ml) ws to trityn yo monomty tr (3.21, 19.5 mmo) n NOH (1.56, 39.0 mmo). Tosy ori (2.89, 20.5 mmo) ws issov in THF (10.0 ml) n ropwis ovr i wit stirrin. T rtion ws t wrm to mint tmprtur ovrnit. Dity tr (20.0 ml) ws tn to t rtion n t mixtur ws tkn up into sprtory unn n prtition. T quous yr ws ws wit ity tr (3 x 5.00 ml) tn t omin orni rtions wr ws wit H2O (3 x 20.0 ml). T orni yr ws ri wit nyrous soium sut, nt n vport to rynss to iv t prout s r oi (4.08, 79 % yi). 1H NMR (400 MHz, CDC3, 25 C): δ (, J = 8.3 Hz, 2H), (, J = 8.0 Hz, 2H), (m, 2H), (r m, 10H), 3.36 (s, 3H), 2.44 (s, 3H). 2-[2-(2-Mtoxytoxy)toxy]tntiott. Tis ompoun ws syntsiz usin prviousy rport prour.6 p-tounsuony trityn yo mty tr (3.80, 14.2 mmo) n potssium tiott (2.02, 17.7 mmo) wr issov in roun ottom sk ontinin ton (150 ml). A rux onnsr ws n t rtion ws stirr viorousy ovrnit t 50 C. Sovnt ws rmov vi vuum n t rsutin mixtur ws issov in ipsi mixtur o 30 ml DCM n 30 ml H2O, tkn up into sprtory unn, n prtition. T quous yr ws ws wit 2 x 30 ml DCM n omin ornis wr ws wit 10 ml rin. T orni yr ws ri wit nyrous soium sut, nt, n vport to rynss to iv t prout s yow oi (2.64, 90 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (r m, 10H), 3.37 (s, 3H), 3.09 (t, J = 6.5 Hz, 2H), 2.33 (s, 3H). 2-[2-(2-Mtoxytoxy)toxy]tntio, meg3sh. Tis ompoun ws syntsiz usin prviousy rport prour.7 Mtno (20.0 ml) n on. HC (1.50 ml) wr to s prssur tu ontinin 2-[2-(2-mtoxytoxy)toxy]tntiott (2.06, 10.0 mmo). T rtion mixtur ws stirr t 100 oc or 3 ours. T rtion ws t oo to mint tmprtur n tn H2O (20.0 ml) ws. Tis mixtur ws xtrt wit 3x 15.0 ml DCM. Comin orni xtrts wr tn ws wit 3x 15.0 ml H2O n 1x 15 ml rin, ri wit nyrous soium S13
14 sut, nt, n vport to rynss to iv t prout s yow oi (1.37, 83 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (r m, 10H), 3.38 (s, 3H), (t, J = 8.2, 6.5 Hz, 2H), 1.58 (t, J = 8.2 Hz, 1H). p-tounsuony ttrtyn yo mty tr. T prour or syntsis o p-tounsuony trityn yo mty tr ws oow. Ttrtyn yo monomty tr (4.23 ) ws us to prpr t prout, otin s r oi (4.18, 66 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (, J = 8.2 Hz, 2H), (, J = 8.1 Hz, 2H), 4.15 (t, J = 9.7 Hz, 2H), (r m, 14H), 3.37 (s, 3H), 2.44 (s, 3H). 2-[2-[2-(2-Mtoxytoxy)toxy]toxy]tntiott. T prour or syntsis o 2-[2-(2mtoxytoxy)toxy]tntiott ws oow. p-tounsuony ttrtyn yo mty tr (2.74 ) ws us to prpr t prout, otin s rk yow oi (2.00, 90 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (r m, 14H), 3.37 (s, 3H), 3.08 (t, J = 6.5 Hz, 2H), 2.33 (s, 3H). 2-[2-[2-(2-Mtoxytoxy)toxy]toxy]tntio, meg4sh. T prour or syntsis o 2-[2(2-mtoxytoxy)toxy]tntio ws oow. 2-[2-[2-(2-mtoxytoxy)toxy]toxy]tntiott (1.31 ) ws us to prpr t prout, otin s p yow oi (851 m, 78 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (r m, 14H), 3.35 (s, 3H), (m, 2H), 1.57 (t, J = 8.2 Hz, 1H). Ttrtyn yo monotosyt. Tis ompoun ws syntsiz usin prviousy rport prour.8. Ttrtyn yo (23.4, 120. mmo) ws to 100 ml roun ottom sk n issov in THF (4.3 ml). NOH (727 m, 18.2 mmo) ws s soution in 4.3 ml H2O. Tosy ori (2.23, 12.0 mmo) ws issov in THF (14.0 ml) n ropwis ovr i wit stirrin. T rtion ws stirr t 0 oc or 3 ours tn iut wit i wtr (70 ml). T mixtur ws S14
15 xtrt wit 3x 45 ml DCM. T omin orni rtions wr ws wit 2 x 130 ml DI wtr, ri wit nyrous soium sut, nt, n vport to rynss to iv t prout s p yow oi (3.69, 87 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (, J = 8.3 Hz, 2H), (, J = 8.5 Hz, 0.58 Hz, 2H), 4.16 (t, J = 4.8 Hz, 2H), (r m, 14H), 2.44 (s, 3H) 2.17 (r s, 1H). Ttrtyn yo monotiott. T prour or syntsis o 2-[2-(2-mtoxytoxy)toxy]tntiott ws oow. Ttrtyn yo monotosyt (3.69 ) ws us to prpr t prout, urtr puriition (oumn romtorpy wit 100 % ty tt) ws rquir to otin t prout s yow oi (1.76, 57 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (r m, 14H), 3.09 (t, J = 6.5 Hz, 2H), 2.33 (s, 3H) 2.29 (r s, 1H). 1-Mrpto-11-yroxy-3,6,9-trioxunn, EG4SH. T prour or syntsis o 2-[2-(2mtoxytoxy)toxy]tntio ws oow. Ttrtyn yo monotiott (200 m) ws us to prpr t prout, otin s p yow oi (95 m, 58 % yi). 1H NMR (400 MHz, CDC3, 25 oc): δ (r m, 14H), (t, J = 8.1 Hz, J = 6.5 Hz, 2H), 2.11 (r s, 1H), 1.62 (t, J = 8.2 Hz, 1H). Gnr prour or tio-n moiition o GHA. A smp o GHA (. 7 m) n DMPA (0.2 q pr GHA rsiu) wr p in 1 rm srw top vi. THF ws tn to iv 4 m/ml poymr onntrtion. T sir tio ws tn vi miropiptt (3 q pr H rsiu) n t soution ws ss y sprin wit N2 or 10 minuts. T vi ws tn ovr wit prim n t soution ws irrit wit UV it or 2.5 ours (Exo Trr Rpti Lmp) n t stir ovrnit. T soution ws tn trnsrr to 2000 MWCO iysis n iyz inst mtno or 24 ours wit on n o iyst, oow y iysis in wtr or 24 ours wit on wtr n. T iyz poymr ws yopiiz to rynss to iv t prout s wit soi. S15
16 meg 3 -G HA 63. T nr prour or tio-n moiition o G HA ws oow. G HA 63 (6.5 m) n meg 3 SH (3 q pr H rsiu) wr us to prpr t prout, otin s wit soi (14.1 m, 83 % yi). 1 H NMR (400 MHz, TFA-, 25 o C): δ (r m, 1H), (r m, 10H), (r m, 5H), (r m 2H), (r m, 6H). meg 4 -G HA 63. T nr prour or tio-n moiition o G HA ws oow. G HA 63 (7.5 m) n meg 4 SH (3 q pr H rsiu) wr us to prpr t prout, otin s wit soi (16.3 m, 89 % yi). 1 H NMR (400 MHz, TFA-, 25 o C): δ (r m, 1H), (r m, 14H), (r m, 7H), (r m, 6H). EG 4 -G HA 63. T nr prour or tio-n moiition o G HA ws oow. G HA 63 (7.5 m) n EG 4 SH (3 q pr H rsiu) wr us to prpr t prout, otin s wit soi (16.3 m, 89 % yi). 1 H NMR (400 MHz, TFA-, 25 o C): δ (r m, 1H), (r m, 14H), (r m, 4H), (r m, 6H). S16
17 G(OA)4-GHA63. T nr prour or tio-n moiition o GHA ws oow. GHA63 (10.8 m) n 1-Tio-β-D-uos ttrtt (3 q pr H rsiu) wr us to prpr t prout, otin s wit soi (38.6 m, 84 % yi). 1H NMR (400 MHz, CDC3/TFA-, 25 oc): δ 5.32 (t, J = 9.3 Hz, 1H), 5.15 (t, J = 9.6 Hz, 1H), 5.03 (t, J = 9.6, 1H), (r, J = 10. Hz, 1H), 4.43 (r s, 1H), 4.24 (r s, 2H), (r, J = 9.8 Hz, 1H), (r, J = 6.8 Hz, 2H), (r m, 12H), (r m, 6H). G-GHA63. Tis prottion oows prviousy rport mto tt ws us or irnt yopoymr.9 G(OA)4-GHA63 (10 m) ws issov in 1:2 DCM:MOH (1 ml). An quous soution o yrzin monoyrt (65 % (w/w), 4 q pr ty roup) ws vi syrin n t mixtur ws stirr. Sorty tr t ition o yrzin monoyrt, wit pripitt orm. T rtion ws t stir ovrnit, tr wi 1-2 rops o ton wr to qun xss yrzin. Et2O (2 ml) ws, t prout ws ntriu t 3000 rpm, n t suprntnt ws isr. T pt ws ws wit tr (2 ml). Sovnt ws rmov vi vuum n t prout ws issov in DI wtr, trnsrr to 2000 MWCO iysis, n iyz or 48 ours wit 2 wtr ns iy. T iyz poymr ws yopiiz to rynss to iv t prout s wit soi (6.2 m, qunttiv yi). 1H NMR (400 MHz, D2O, 25 oc): δ (r, J = 9.1 Hz, 1H), 3.95 (r s, 1H), (r, J = 11.4 Hz, 1H), (r m, 1H), (r m, 3H), (r m, 1H), 2.67 (r s, 2H), (r m, 6H). meg4-(r-gha)43. T nr prour or tio-n moiition o GHA ws oow. (r-gha)43 (8.0 m) n meg3sh (6 q pr r-h rsiu) wr us to prpr t prout, otin s wit soi (16.3 m, 68 % yi). (93 % untioniztion, trmin y omprison o kn 2H intr S17
18 (5.17 ppm) to t intr rom t oiotyn yo roup ( )). 1H NMR (400 MHz, TFA-, % Trnsmittn 25 oc): δ (r m, 1H), (r m, 14H), (r m, 7H), (r m, 6H) m m Wvnumr (m-1) Fiur S7. Soi stt FT-IR o meg4-(r-gha)43. T Ami I n Ami II ns t 1625 n 1521 m-1, rsptivy, r rtristi o β-st onormtion. Sonry moiition o tio-n onjut poypptis meg4-gham63. meg4-gha63 (6.6 m) ws suspn in 0.2 M ormi i (330 µl). Mty ioi ws vi syrin (6 q pr meg4-h rsiu), t rtion ws tn ovr n stirr viorousy or 72 ours. T rtion mixtur ws trnsrr to 2000 MWCO iysis n iyz inst 0.1 M NC or 24 ours, oow y DI wtr or 24 ours wit 2 wtr ns iy. T iyz poymr ws tn yopiiz to rynss to iv t prout s trnsunt wit soi (7.5 m, 99 % yi). 1H NMR (400 MHz, D2O, 25 oc): δ 4.36 (r s, 1H), 4.05 (r t, J = 5.1 Hz, 3H), (r m, 14H), (r m, 5H), 3.00 (s, 3H), (r m, 6H). meg4-ghao63. meg4-gha63 (11 m) n CSA (1.6 m) wr issov in DI wtr (1.1 ml). An quous soution o TBHP (70 % (w/w), 16 q pr meg4-h rsiu) ws tn. T rtion ws t stir ovrnit n qun wit 1-2 rops o sturt quous soium tiosut soution. T rtion mixtur ws trnsrr to 2000 MWCO iysis n iyz inst DI wtr or 48 ours wit 2 wtr ns iy. T iyz poymr ws yopiiz to rynss to iv t prout s S18
19 wit soi (8.7 m, 75 % yi). 1 H NMR (400 MHz, D 2 O, 25 o C): δ 4.19 (r s, 1H), (r m, 14H), 3.27 (s, 3H), (r m, 1H), (r m, 1H), (r m, 2H), (r m, 6H). 4. Syntsis n moiition o ok opoypptis Exmp iok opoyppti syntss Poy(L-mtionin) 50 -ok-poy(l-omoyyin) 24, M 50 G HA 24. A poymriztion rtions wr prorm in initron i ov ox usin nyrous sovnts. To soution o Mt NCA in THF (98.0 m, 550 µmo, 50 m/ml) ws soution o Co(PM 3 ) 4 in THF (515 µl, 28 µmo). On mix, t rtion ws t stn t mint tmprtur or 1 our n omption o poymriztion ws onirm y FTIR. An iquot (203 µl) ws rmov rom t rtion n npp wit PEG-NCO to trmin DP o t irst ok (oun DP = 50) (s mto ov). To t rminin poymriztion soution ws soution o H NCA in THF (39.8 m, 2.60 µmo, 50 m/ml). T rtion ws t stn or 1 our n omption o poymriztion ws onirm y FTIR. T rtion ws rmov rom t ov ox n 1-2 rops o 3 M HC wr. T poyppti ws tn pripitt wit DI wtr, ntriu t 3000 rpm, n t suprntnt ws isr. T pt ws ws 3 tims wit DI wtr n tn yopiiz to yi poy(l-mtionin) 50 -ok-poy(l-omoyyin) 24, M 50 G HA 24 (omposition trmin y 1 H NMR), s wit soi (94.4 m, 99 % yi). 1 H NMR (400 MHz, TFA, 25 o C): δ (r m, 1H), (r m, 2H), (r m, 2H), (m, 1H), (r m, 4H), (r m 12H), (r m, 2H). Poy(L-omoyyin) 71 -ok-poy(l-mtionin) 36, G HA 71M 36. A poymriztion rtions wr prorm in initron i ov ox usin nyrous sovnts. To soution o H NCA in THF (20.1 m, 130 µmo, 25 m/ml) ws soution o Co(PM 3 ) 4 in THF (119 µl, 6.47 µmo). On mix, t rtion ws t stn t mint tmprtur or 1 our n omption o poymriztion ws onirm y FTIR. An iquot (370 µl) ws rmov n npp wit PEG-NCO to trmin DP S19
20 o t irst ok (oun DP = 71). To t rminin poymriztion soution ws soution o Mt NCA in THF (6.83 m, 39.0 µmo, 50 m/ml). T rtion ws t stn or 1 our n omption o poymriztion ws onirm y FTIR. T rtion ws rmov rom t ov ox n 1-2 rops o 3 M HC wr. T poymr ws tn pripitt wit DI wtr, ntriu t 3000 rpm, n t suprntnt ws isr. T pt ws ws 3 tims wit DI wtr n tn yopiiz to yi Poy(L-omoyyin) 71 -ok-poy(l-mtionin) 36, G HA 71M 36 (omposition trmin y 1 H NMR) s wit soi (13.4 m, 97 % yi). 1 H NMR (400 MHz, TFA-, 25 o C): δ (r m, 2H), (r m, 4H), (r m, 1H), (r m, 2H), (r m, 2H), (r m, 9H), (r m, 4H). Moiitions o iok opoypptis G(OA) 4 -G HA 27M 80. G HA 27M 80 (14.4 m), 1-Tio-β-D-uos ttrtt (8 q pr H rsiu) n DMPA (2.92 m, 0.4 q pr H rsiu) wr p in 1 rm srw top vi. THF ws tn to iv opoymr onntrtion o 10 m/ml. T soution ws tn ss vi sprin wit N 2 or 10 minuts. T vi ws tn ovr wit prim n t soution ws irrit wit UV it or 2.5 ours (Exo Trr Rpti Lmp) n t stir ovrnit. T soution ws tn trnsrr to 2000 MWCO iysis n iyz inst mtno or 24 ours wit on n o iyst, oow y iysis inst wtr or 24 ours wit on wtr n. T iyz poymr ws yopiiz to rynss to iv t prout s wit soi (20.4 m, 82 % yi). 1 H NMR (400 MHz, CDC 3 /TFA-, 25 o C): δ 5.34 (t, J = 9.2 Hz, 1H), 5.18 (t, J = 9.6 Hz, 1H), 5.05 (t, J = 9.6, 1H), (r, J = 9.6 Hz, 1H), 4.43 (r s, 1H), 4.26 (r s, 5H), (r, J = 10.1 Hz, 1H), (r m, 8H), (r m, 27H), (r m, 6H). S20
21 G(OA) 4 -G HA 27M M 80. G(OA) 4 -G HA 27M 80 (11.7 m) ws suspn in DI wtr (1.2 ml). Mty ioi ws vi syrin (6 q pr Mt rsiu), t rtion ws tn ovr n stirr viorousy or 72 ours. T rtion mixtur ws trnsrr to 2000 MWCO iysis n iyz inst 0.1 M NC or 24 ours, oow y DI wtr or 24 ours wit 2 wtr ns iy. T iyz poymr ws tn yopiiz to rynss to iv t prout s trnsunt wit soi (13.0 m, 95 % yi). 1 H NMR (400 MHz, TFA-, 25 o C): δ (r m 1H), (r m, 1H), (r m, 1H), (r m, 3H), (r m, 1H), (r m, 1H), (r m, 2H), (r m, 1H), (r, J = 45.2 Hz, 6H), (r, J = 5.8 Hz, 18H), (r m, 8H), (r m, 12H), (r m, 6H). M O 42G HA 19. A soution o yron proxi:ti i in DI wtr (3 %:1.5 % (v/v), 2.61 ml) ws to vi ontinin M 42 G HA 19 (31.3 m). T suspnsion ws stirr viorousy ovrnit, riy vortx tr 18 ours n t stir or 6 mor ours. T rtion ws qun wit 1-2 rops o quous sturt soium tiosut soution n tn trnsrr to 2000 MWCO iysis. T rtion mixtur ws iyz inst wtr or 48 ours wit two wtr ns iy. Lyopiiztion yi t prout s wit, uy soi (32.2 m, 95 % yi). 1 H NMR (400 MHz, TFA-, 25 o C): δ (r m, 1H), (r m, 2H), (r m, 2H), (r m, 1H), (r m 5H), (r, J = 7.9 Hz, 7H), (r m, 5H), (r m, 4H). S21
22 MO42mEG4-GHA19. MO42GHA19 (8.0 m), n DMPA (1.9 m, 0.4 q pr H rsiu) wr p in 1 rm srw top vi. A mixtur o 25% THF in AOH ws tn to iv poymr onntrtion o 4 m/ml. meg4sh ws tn vi miropiptt (10 q pr H rsiu) n t soution ws ss vi sprin wit N2 or 10 minuts. T vi ws tn ovr wit prim n t soution ws irrit wit UV it or 2.5 ours (Exo Trr Rpti Lmp) n t stir ovrnit. T soution ws tn trnsrr to 2000 MWCO iysis n iyz inst mtno or 24 ours wit on n o iyst, oow y iysis in wtr or 24 ours wit on wtr n. T iyz poymr ws yopiiz to rynss to iv t prout s wit soi (10.3 m, 86 % yi). 1H NMR (400 MHz, TFA-, 25 oc): δ (r m, 2H), (r m, 1H), (r m, 14H), (r m, 9H), (r, J = 8.1 Hz, 6H), (r m, 4H), (r m, 2H), (r m, 6H). MO42mEG4-GHAM19. MO42mEG4-GHA19 (7.7 m) ws suspn in 0.2 M ormi i (520 µl). Mty ioi ws vi syrin (6.6 q pr meg4-h rsiu), t rtion ws tn ovr n stirr viorousy or 72 ours. T rtion mixtur ws trnsrr to 2000 MWCO iysis n iyz inst 0.1 M NC or 24 ours, oow y DI wtr or 24 ours wit 2 wtr ns iy. T iyz poymr ws tn yopiiz to rynss to iv t prout s trnsunt wit soi (8.3 m, 99 % yi). 1H NMR (400 MHz, TFA-, 25 oc): δ (r m, 2H), (r m, 1H), (r m, 14H), (r m, 5H), (r s, 3H), (r, J = 7.9 Hz, 6H), (r m, 2H), (r m, 2H), (r m, 6H). S22
23 [Θ] x = M 42 G HA 19 = M O 42 meg 4 -GHA 19 = M O 42 meg 4 -GHAM 19 Fiur S8. Cirur iroism sptr o M 50 G HA 24 n its rivtiv ok opoypptis t 0.1 m/ml, 20 o C. M 42 G HA 19 (u, in THF), M O 42mEG 4 -G HA 19 (r, in DI wtr, 25% α-ix), M O 42mEG 4 - G HAM 19 (k, in DI wtr, 12% α-ix). T rivtiv M O 42G HA 19 possss poor souiity in ot orni n quous sovnts n ws not nyz. Rrns 1. () O Donn, M. J.; Wojiowski, K.; Gosz, L.; Nvrro, M.; Sint, F.; Antoin, J-P. Syntsis. 1984, 4, () Guinn, R. M.; Mrot, A. O.; Tyor, J. R.; Sumr, M.; Crk, D. S.; Bn, H. W. Biopoymrs, 1995, 35, () Crk, T. D.; Giri, M. R. J. Am. Cm. So. 1995, 117, () Cnut, H. K.; Dmr, J.; Witsis, G. M. J. Am. Cm. So. 1989, 111, Krmr, J. R.; Dmin, T. J. Biomromous 2010, 11, Brzzinsk, K. R.; Curtin, S. A.; Dmin, T. J. Mromous 2002, 35, Yosimoto, M.; Hon, K., Kurosw, S.; Tnk, M. J. Pys. Cm. C. 2014, 118, Goo, P.; Workntin, M. S. Lnmuir 2012, 28, Ki, D. J.; Grn, J. B.; Gonz, F.; Brook, M. A.; Drvi, T. R. Or. Ltt. 2011, 13, Wvnt (nm) 8. DForst, C. A.; Tirr, D. A. Nt. Mtr. 2015, 14, Krmr, J. R.; Dmin, T. J. J. Am. Cm. So. 2012, 134, S23
24 NMR Sptr Dt j j i,, i,, S24
25 , S25
26 i j k i,k,j, S26
27 , Wtr S27
28 ,, S28
29 j i k k j i j i k k S29
30 ,, S30
31 j k i, k j i j k i k S31
32 S32
33 ,, THF Wtr,, DCM Wtr S33
34 ,,,, S34
35 ,,,, S35
36 ,,,, S36
37 ,, i j,,i,j,, S37
38 i j,,i,,j,,,,i i,,, S38
39 i j k i k j,,,,i 93 % Funtioniz j i Unrt kn,,j,, S39
40 j i k i,k j,, i,k j,i,j k,, S40
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