Supporting Information. Templating A Polymer-Scaffolded Dynamic Combinatorial Library

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Mervin Ross
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1 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry 2011 upportn Informton Tmpltn A Polymr-ffol Dynm Comntorl Lrry Clr. Mon, Alxnr W. Jkson, Bnjmn. Murry n Dv A. Fulton* Cml nosn Lortory, ool of Cmstry, wstl Unvrsty, wstl upon Tyn, E1 7RU, UK ml:..fulton@nl..uk Gnrl Exprmntl All mls, nlun Grr s rnt T (1) wr purs from m-alr or Alf Asr n wr us s rv wtout furtr purfton., -mtylrylm ws purf y vuum stllton t 60 C. 1 n 13 C MR sptr of syntss ompouns wr ror on Brukr Avn 300 sptromtr t 300 n 75 Mz rsptvly, or on JEL EC-400 sptromtr t 400 Mz n 100 Mz, wt t rsul solvnt snl s n ntrnl stnr. FTIR sptrosopy ws prform on Vrn 800 FTIR nstrumnt (Vrn In.). -rsoluton mss sptromtry ws prform on Wtrs LCT prmr mss sptromtr (Wtrs In.). Gl prmton romtorpy (GPC) ws onut on Vrn Protr nstrumnt (Vrn In.) qupp wt Vrn 325 UV-Vs ul wvlnt ttor (254 nm), Dwn los II mult-nl lsr lt sttrn ttor (Wytt Tnoloy Corp.), Vsotk 3580 ffrntl RI ttor, n pr of PL l 5 µm Mx D mm olumns wt ur olumn (Polymr Lortors In.) n srs. r monosprs mtyl mtrylt stnrs (Alnt Tnolos) wr us for lrton. Dt ollton ws prform wt Glx softwr (Vrn In.) n romtorms nlyz wt t Crrus softwr (Vrn In.) n Astr softwr (Wytt Tnoloy Corp.). 1 MR sptr of P-DCLs wr msur usn JEL Lm sptromtr ( 1 t 500 Mz), n nlys usn Mstrov. P-DCLs wr prpr so s to ontn 50.0 mm onntrtons of ylyrzs 1 n 2, wt P1 prsnt n 3.1 mm onntrton. Equlrton to 1.0:1.0 rto of 1 to 2 n soluton ws onfrm y 1 MR sptrosop nlyss pror to ton of BA or poly(soum-4-styrn sulpont) (2.5 m). ptr wr ror ovr pro of 17 ftr tmplt ton. Exprmntl Prours: () 3 () () 4 (v) M1 1. yntss of -tylrylm-2-(4-formylnzm) (M1): () C(C 3 ) 3, M, 2 4, 80 C, 48. () 1,2-mnotn, 130 C, 24. () Aryloyl lor, Et 3, C 2 Cl 2, 0 C, 16. (v) 1M Cl (q), 2.

2 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry 2011 Mtyl 4-(mtoxymtyl)nzot [1] (3): A soluton of 4-roxynzly (15.4, mmol), trmtylortoformt (32.7, mmol) n 2 4 (8 rops) n M (100 ml) ws t unr rflux ontons for 48. T rton mxtur ws trnsfrr to sprtn funnl wt sturt C 3(q) (100 ml). T quous lyr ws xtrt wt C 2 Cl 2 (3 150 ml). T orn xtrts wr omn n r ovr 2 4, fltr n vport to rynss to ffor ru lqu w ws purf y vuum stllton to ffor t ttl prout s lr lqu (19.8, 92%). 1 MR (300 Mz, CDCl 3 ): δ 3.30 (s, 6, C(C 3 ) 2 ), 3.89 (s, 3, C 3 ), 5.42 (s, 1, C(C 3 ) 2 ), 7.51 (, 2, Ar, J = 8.1 z), 8.02 (, 2, Ar, J = 8.1 z). 13 C MR (75 Mz, CDCl 3 ): δ 52.2, 53.0, 103.0, 127.1, 129.8, 130.8, 143.8, Etylrylm-2-(4-(mtoxymtyl)nzm) (4): A soluton of mtyl 4-(mtoxymtyl)nzot 1 (6.0, 28.5 mmol) n 1,2-mnotn (100 ml) ws t unr rflux for 24 tn vport to rynss. T vsous yllow ol otn ws ssolv n C 2 Cl 2 (100 ml) n Et 3 (5.7, 56.3 mmol). T soluton ws ool to 0 C n n t. Aryloyl lor (2.6, 28.5 mmol) n C 2 Cl 2 (50 ml) ws ropws ovr 30 mn. T rton ws strr ovrnt t room tmprtur tn trnsfrr to sprtn funnl wt sturt C 3(q) (150 ml). T quous lyr ws xtrt wt C 2 Cl 2 (2 150 ml). T orn xtrts wr omn n r ovr 2 4, fltr n vport to rynss to ffor ru sol w ws purf y olumn romtorpy [ 2, EtA-Et 3 (95:5)] to ffor t ttl prout s wt sol (3.3, 40 %). 1 MR (300 Mz, CDCl 3 ): δ 3.28 (s, 6, C(C 3 ) 2 ), 3.52 (m, 4, (C 2 ) 2 ), 5.37 (s, 1, C(C 3 ) 2 ), 5.58 (, 1, J = 9.6 z), 6.14 (, 1, J = 17.1 z), 6.23 (, 1, J = 17.1 z), 7.37 (s, 1, ), 7.45 (, 2, Ar, J = 8.1 z), 7.79 (, 2, Ar, J = 8.1 z), 7.84 (s, 1, ). 13 C MR (75 Mz, CDCl 3 ): δ 41.3, 53.1, 103.1, 127.3, 128.2, 130.0, 131.3, 134.6, 142.1, 167.5, FT-IR (wvnumr, m -1 ): 3290 ( ), 3096 (C, lkn), 2947 (C, lkyl), 1634 (C=), 1593 (C=), 1448 (C=C, romt), 1413 (C=C, romt). RM + C : Tortl: Atul: Etylrylm-2-(4-formylnzm) (M1): A soluton of -tylrylm-2-(4-(mtoxymtyl)nzm) 2 (1.4, 4.8 mmol) n 1M Cl (q) (20 ml) ws strr t room tmprtur for 2 tn nutrlz wt sturt C 3(q) (100 ml). T quous lyr ws xtrt wt EtA (3 150 ml). T orn xtrts wr omn n r ovr M 4, fltr n vport to rynss to ffor t ttl prout s wt sol (0.99, 84 %). 1 MR (300 Mz, DM- 6 ): δ 3.72 (m, 4, (C 2 ) 2 ), 5.59 (, 1, J = 9.6 z), 6.09 (, 1, J = 17.1 z), 6.23 (, 1, J = 17.1 z), 7.99 (, 2, Ar, J = 8.4 z), 8.03 (, 2, Ar, J = 8.4 z), 8.23 (s, 1, ), 8.79 (s, 1, ), (s, 1, C). 13 C MR (75 Mz, DM- 6 ): δ 38.7, 125.2, 128.3, 129.6, 132.3, 138.2, 140.1, 165.5, 166.1, FT-IR (wvnumr, m -1 ): 3264 ( ), 3091 (C, lkn), 2943 (C, lkyl), 1699 (C=, ly), 1627 (C=, m), 1549 (C=, m), 1447 (C=C, romt), 1414 (C=C, romt). RM + C : Tortl: Atul:

3 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry f f + ppm (f1) MR sptrum (CDCl 3, 300 Mz) of M1. + AIB DMF 70 o C C M1 P1 3. yntss of ly funtonl opolymr P1. Aly-Funtonlz Copolymr (P1): -1-Doyl- -(α,α-mtyl-α -t )trtoront [2] (DDMAT) (1 q, 34.2 m, mmol) n AIB (0.2 q, 3.08 m, 19 µm) wr to smll slnk tu., - Dmtylrylm (DMA) (80 q, 0.745, 7.52 mmol) n -tylrylm-2-(4- formylnzm) (M1, 20 q, 0.463, 1.88 mmol) wr tn follow y DMF (3 ml). T rton mxtur ws ss fv tms, n tn t vssl ws kfll wt 2, pur wt 2, n llow to wrm to room tmprtur. T rton mxtur ws tn pl n n ol t t 70 C, n t polymrzton ws qun ftr 22. T rton mxtur ws ssolv n mnml mount of TF n ropws to lr xss of -ol tyl tr. T polymr prptt ws tn solt y fltrton n t prptton ws rpt for ryn unr vuum. Polymr P1 ws otn s pl yllow sol (1.05 ). 1 MR (300 Mz, CDCl 3 ): (r, CC 2, polymr kon), (r, CC 2, polymr kon), 2.88 (r, (C 3 ) 2 ), (r, (C 2 ) 2 ), 7.88 (r, Ar), 8.07 (r, Ar), 8.59 (r, ), (r, Ar). T omposton of P1 n trmn y omprn t ntrton of t ly protons of M1 wt t ntrton of t (C 3 ) 2 protons of DMA. T monomr omposton ws trmn to 5:1

4 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry 2011 DMA:M1 (monomr omposton ws not ntl to t f rto of 4:1 DMA:M1 s onsqun of t ffrn n rtvty of t two monomrs). 3 C-C f f f ppm (f1) MR sptrum of P1 (300 Mz, CDCl 3 ) Rspons (V) Rtnton Tm (mn) 5. Gl prmton romtorpy (GPC) rfrtv nx (RI) tr n DMF (0.6 ml/ mn) of P1. polymr n trnsfr nt DDMAT (1 q) monomrs nttor solvnt tm () tmp ( C) M n ( mol -1 ) M n ( mol -1 ) P1 DMA AIB (80 q) (0.2 q) M1 (20 q) 6. Crtrzton of opolymr P1. As trmn y 1 MR sptrosopy M w ( mol -1 ) PDI (M w/m n) DMF ,850 18,500 21, As trmn y l prmton romtorpy n DMF (0.6 ml/ mn) lrt nst nr monosprs mtyl mtrylt stnrs. AIB: zos(soutyrontrl), DMF: mtylformm, DMA:, -mtylrylm, DDMAT: -1-oyl- -(α,α-mtyl-α -t )trtoront.

5 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry 2011 () () () (v) yntss of 2-(2-yroxytoxy)toyrz (2): (), RT to 100 C, 3. () 2-romot, 100 C, 48. () , M, rflux, 4. Mtyl 2-(2-yroxytoxy)tt (5) oum (4.6, 200 mmol) ws n smll ps to tyln lyol (50 ml, 897 mmol) t room tmprtur unr 2, tn strr untl omonous lqu ws otn. T yllow lqu ws t to 100 C for 3 follow y t ton of romot (13.9, 100 mmol) to yl mmtly rk orn-olour mxtur. T rton ws t t 100 C for furtr 48 follow y rmovl of xss tyln lyol y vuum stllton. T rmnn rsu ws tkn up n Cl (37%, 60 ml) tn fltr n t fltrt r unr ru prssur to lv vsous rown ol. T ol ws ssolv n M (100 ml) n tn 2 4 (5 ml) ws n t rsultn soluton ws t t rflux for 12 tn ool to room tmprtur n nutrls y t ropws ton of st. C 3 soluton untl ffrvsn s. T soluton ws onntrt to volum of 50 ml unr ru prssur, lut y t ton of C 2 Cl 2 (100 ml) tn xtrt wt rn (100 ml). T rn ws kws wt C 2 Cl 2 (3 x 50 ml) n t omn orn solutons wr r unr ru prssur to ffor t ru prout s rown ol w ws furtr purf y olumn romtorpy on sl (100% C 2 Cl 2 ) to yl t sr prout s wt sol (1.22, 9.1 mmol, 9 %); R F = 10/37 (C 2 Cl 2 :M 10:1.5, sl); 1 MR (CDCl 3, 400 Mz): δ 4.08 (s, 2, -C=C 2 -), 3.69 (m, 5, C 3 - n C 2 -C 2 -), 3.59 (m, 2, -C 2 -C 2 -), 3.32 (s r, 1, -); 13 C MR (CDCl 3, 100 Mz): δ (C=), 73.2, 68.3, 61.5, 51.9 (C 3 ); RM (CI+) C [M + 4 ] + : Tortl: Atul: ; m.p C 2-(2-yroxytoxy)toyrz (2) A soluton of yrzn monoyrt (0.6 ml, 13.6 mmol) n mtyl 2-(2-yroxytoxy)tt (1.22, 9.1 mmol) n M (50 ml) ws t t rflux for 4 tn r unr ru prssur to ffor rystlln wt sol. T sol ws suspn n C 2 Cl 2 (50 ml), sont for 20 mn tn fltr. Ts pross ws rpt tw t w pont t sol ws ju pur y TLC nlyss to yl t sr prout s rystlln wt sol (0.683, 5.1 mmol, 56 %); R F = 7/54 (C 2 Cl 2 :M 10:1.5, sl); 1 MR (DM- 6, 300 Mz): δ 9.01 (s r, 1, ), 4.80 (t, 1, J = 6.0 z, ), 4.26 (s r, 2, 2 ), 3.89 (s, 2, -C=C 2 -), (m, 4, C 2 -C 2 -); 13 C MR (DM- 6, 100 Mz): δ (C=), 72.9, 69.4, 60.1 ; RM (E + ) C : Tortl: Atul : ; m.p C.

6 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry MR sptrum (400 Mz, CDCl 3 ) of mtyl 2-(2-yroxytoxy)tt (5) C MR sptrum (100 Mz, CDCl 3 ) of mtyl 2-(2-yroxytoxy)tt (5)

7 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry f f MR sptrum (300 Mz, DM- 6 ) of 2-(2-yroxytoxy)toyrz (2) C MR sptrum (100 Mz, DM- 6 ) of 2-(2-yroxytoxy)toyrz (2)

8 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry 2011 CM_3143_0 nl Puls Exprmnt C X M 2 Y C 2 D 4 A/A Cl M M 3 Cl f f f j j j MR sptrum of P-DCL (400 Mz, D 2 ) pror to ton of tr tmplt. CM_393_16 nl Puls Exprmnt C X M 2 Y C 2 D 4 A/A Cl M 3 2 M 3 Cl f f + j j 2 f + + j : 1 MR sptrum of P-DCL (400 Mz, D 2 ) 17 ftr ton of ovn srum lumn. 1.0

9 upplmntry Mtrl (EI) for Cml Communtons Ts journl s T Royl oty of Cmstry 2011 CM_3143_16 nl Puls Exprmnt C X M 2 Y C 2 D 4 A/A Cl M M 3 Cl f f f j j j : 1 MR sptrum of P-DCL (400 Mz, D 2 ) 17 ftr ton of poly(soum-4-styrn sulpont).

Catalytic S N Ar of Unactivated Aryl Chlorides ESI

Catalytic S N Ar of Unactivated Aryl Chlorides ESI Eltron Supplmntry Mtrl (ESI) or CmComm. Ts journl s T Royl Soty o Cmstry 2014 Ctlyt S Ar o Untvt Aryl Clors ESI Tl o Contnts 1. Prour n Full Tl o Contons - Prour S1 - Intl solvnt srn (no tlyst) - Solvnt