O p t i c a l l y
A c t i v e
P o l y m e r s
Katsuhiro l n o m a t a Department of Polymer Chemistry, Tokyo Institute of Technology, Tokyo, Japan Akihiro Abe Department of Industrial Chemistry, Tokyo Institute of Polytechnics, Atsugi, Japan A. Abbreviations used B. Optically Active Polymers from Chiral Monomers Table 1. Main-Chain Acyclic Carbon Polymers 1.1. Poly(alkenes) 1.2. Poly(acrylics) and Related Polymers 1.3. Poly(methacrylics) and Related Polymers 1..4. Poly(vinyl ethers), Poly(vinyl ketones), and Poly(vinyl esters) 1.5. Poly(styrenes), Poly(carbazoles) 1.6. Poly(dienes) 1.7. Poly(isonitriles) 1.8. Poly(alkynes) 1.9. Poly(maleimides) and Related Polymers 1.10. Other Compounds Table 2. Main-Chain Acyclic Heteroatom Polymers 2.1. Poly(oxides) 2.2. Poly(esters) 2.3. Poly (su If ides), Poly(thioesters) 2.4. Poly(urethanes), Poly(ureas) 2.5. Poly(amides) 2.6. Poly(isocyanates) 2.7. Poly(imines) 2.8. Poly(amino acids) Table 3. Poly(saccharides) C. Optically Active Polymers from Achiral Monomers Table 4. Main-Chain Acyclic Carbon Polymers 4.1. Poly(acrylics) and Related Polymers 4.2. Poly(methacrylics) and Related Polymers 4.3. Polytvinyl ethers)
VII-715 VII-716 VII-716 VII-716 VII-716 VII-717 VII-718 VII-719 VII-720 VII-720 VII-721 VII-722 VII-723 VII-723 VII-723 VII-724 VII-725 VII-725 VII-726 VII-728 VII-728 VII-729 VII-732 VII-733 VII-733 VII-733 VII-734 VII-735
4.4. Poly(styrenes) 4.5. Poly(dienes) 4.6. Poly(isonitriles) 4.7. Poly(maleimides) 4.8. Other Compounds Table 5. Main-Chain Acyclic Heteroatom Polymers 5.1. Poly(oxides) and Poly(sulfides) 5.2. Poly(isocyanates) D. References
VII-735 VII-735 VII-736 VII-736 VII-737 VII-737 VII-737 VII-738 VII-739
By definition the optical activity, [M] A, of polymers and their low molecular weight analogs is given by [M] A = [a\x x (mean residue weight)/100
A. ABBREVIATIONS USED AcAc Acetylacetonate AIBN Azobisisobutyronitrile BPO Benzoyl peroxide DBP Dibenzoyl peroxide DCA Dichloroacetic acid DCM Dichloromethane DDB 2,3-Dimethoxy-1,4-bis(dimethylamino)butane DMAc Dimethylacetamide DMF Dimethylformamide DMSO Dimethylsulfoxide DPEDA-Li iV^/V'-diphenylethylenediamine monolithium amide EDC Ethylene dichloride M Monomer MC Model compound NCA iV-Carboxylic anhydride P Polymer RT Room temperature TMEDA A^N,A/^JV'-tetramethylethylenediamine TCA Trichloroacetic acid TFA Trifluoroacetic acid TFEL Trifluoroethanol THF Tetrahydrofuran
B. OPTICALLY ACTIVE POLYMERS FROM CHIRAL MONOMERS TABLE 1.
MAIN-CHAIN ACYCLIC CARBON POLYMERS
Polymer Catalyst or initiator 1.1.
Polymerization system
Polymer (P) values
T(0C)
[M] D
Benzene
30-40
-20to -120 -35.3 to -144 - Ill
Isooctane
RT
Isooctane Isooctane Isooctane
Solvent
Monomer (M) or model compound (MC) values [M)0
Optical activity measured Solvent
T (0C)
Refs.
POLY(ALKENES)
Poly[(/?)(- )3,7-dimethyl-1 -octene] Al(Z-C4Hg)3ZTiCl4 Al(Z-C 4 H 9 ) 3/TiCl3 LiAlH 4/TiCl 4/monomer Poly[(S)( + )5-methyl-1 -heptene] Al(J-C4Hg)3ZTiCl3 Poly [(S)( + )4-methyl-l -hexenej Al(I-C4Hg)3ZTiCl4 Al(z-C4H9)3/TiCl3 Poly[(£)( + )6-methyl-1 -octene] Al(Z-C4Hg)3ZTiCl3 Poly[(S)( + )3-methyM-pentene] Al(Z-C4H9)3/TiCl4 Al(Z-C 4 Hg) 3 ZTiCl 3 Poly [(5)5-pheny 1-1-heptene] Al(Z-C 4 Hg) 3 ZTiCl 3 PoIy[Cff)4-phenyl-1 -hexene] Al(Z-C 4 H 9 ) 3 /TiCl 3
4,7
14.4 (MC) 14.4 (MC) 8.88 (MC)
Toluene Toluene Carbon tetrachloride
27.4-68.1
11.7 (MC)
Benzene
RT RT
205-288 149-279
21.3 (MC) 21.3(MC)
Benzene (MC); toluene (P) Benzene (P)
25 25
2-6,9
RT
16.0 20.4
13.3(MC) 13.3(MC)
Benzene
25
4 5
20-25
29.4-158
- 11.4 (MC)
Tetralin (P)
20-25
75.8-157 161
- 11.4 (MC)
Tetralin (P)
25 (P); 20 (MC) 2-6, 8,9 25 (P); 20 (MC) 5
-78.1
6.25
25 25 25
2-6
26.6
4.80 (M)
Cyclohexane (P); neat (M)
25
118
60
-61.6
- 8.99 (M)
Chloroform (P); neat (M)
25
118
Dioxane
60
-21.0
-21.0 (MC)
Dioxane
25
12
65 60 35 -70 -78
-46.1 -47.2 -47.4 -43.0 -47.2
Toluene Toluene Toluene Toluene Toluene
25 25 25 25 25
10
Benzene Toluene Toluene Toluene Dioxane
50-100 RT
23.4 17.9
55.5 (M) 42.2 (M)
Chloroform (P); neat (M) Dioxane
21 (P); 22 (M) 25
13 14
Dioxane
RT
15.3
37.4 (M)
Dioxane
30
13
Benzene
50 60
Benzene Chloroform (P); neat (M)
22 25
11 215
2,2,4-Trimethylpentane 25-60 2,2,4-Trimethylpentane
1.2. POLY(ACRYLICS) AND RELATED POLYMERS Poly(acryloyl-L-glutamic acid) AIBN Poly(L-bornyl acrylate) AIBN AIBN AIBN C 6 H 5 MgBr UV benzoin Po\y(d-sec-butyl a-chloroacrylate) BPO BPO Poly{d-sec-butyl a-bromoacrylate) BPO Poly(L-menthyl acrylate) AIBN AIBN
-79.0 -73.9
- 56.4 (M) - 56.4 (M) - 56.4 (M) - 56.4 (M) - 56.4 (M)
-99.3(M) - 88.3 (M)
PoIyU + ^-methyl-Af-a-methylbenzyl-acrylamidel AIBN Toluene n-BuLi Toluene C 6 H 5 MgBr Toluene Poly[( - W-propyl-N-a-methylbenzyl-acrylamide] Toluene AIBN Toluene /1-BuLi
(M) (M) (M) (M)
Benzene Benzene Benzene Benzene
25 25 25 25
29
- 167 -318
_ 444 (M) _ 444 (M)
Benzene Benzene
25 25
29
Toluene
20
10
-70.8
-50.1 (M) - 32.2 (M) -28.8(M)
EDC (P); ethanol (M) Benzene
25 20
23,24 25-27
- 8.6 (M)
Benzene
19
26
DCM
20
17,18
Benzene (M); methanol -0.01% CH3SO3H(P) Methanol- 0.01%CH3SO3H after 1 h Methanol-13%CH3SO3H
25
225
25
Benzene Chloroform Chloroform Benzene Benzene Chloroform
25 20 20 25 25 25
16,11
Dioxane
25
28
Water
20
119
Water
20
215
Dioxane
25
28
Water
20
222
Dioxane Dioxane Dioxane Dioxane (P); neat (M)
25 25 25 25
19-21
Chloroform (P); isooctane (M) 20 Chloroform (P); isooctane (M) 20
16,22
60 22 -50 -50
278 397 366 337
70 22
504 504 504 504
1.3. POLY(METHACRYLICS) AND RELATED POLYMERS Poly(L-bornyl methacrylate) 55 Benzene AIBN PoIy(1,2; 5,6-diisopropylidene-D-glucofuranosyl-3-methacrylate) Benzene 80 BPO 40-50 AIBN Benzene Poly(2,3 ; 4,6-diisopropylidene-L-sorbofuranosyl-1 -methacrylate) Carbon tetrachloride 60 AIBN PoIyK + M ,3-dimethylbutyl methacrylate] BPO 82-110 PoIyK + )(S)-diphenyl(l-methyl-pyrrolidin-2-yl)methyl methacrylate] DPEDA-Li/TMEDA Toluene -78
-49.0 -48.4 -84.5 18.2 780(LaJ 365 )
23.4 (MC) 30.9
43.5 (MC) -82.2(M)([aJ 365 )
-410(LaJ 365 ) 779(LaJ 365 ) Poly( 1 -menthyl methacrylate) AIBN Benzene BPO C 6 H 5 MgBr Toluene C 6 H 5 MgBr Toluene 7-Ray BuLi THF Poly(methacryloyl-D-alanine) AIBN Dioxane Poly(Af-methacryloyl-L-alanine) AIBN Dioxane Pory(N-methacryloyl-L-asparagine) AIBN Dioxane PoIy(methacryIoyl-L-glutamic acid) AIBN Dioxane Poly(s-N-methacryloyl-L-lysine] Potassium persulfate Water Poly( 1 -a-methylbenzy 1 methacrylate) UV AIBN UV benzoin /i-BuLi Toluene AIBN Dioxane Poly(2-methylbutyl methacrylate) BPO C 6 H 5 MgBr Toluene PolyL(5)4-methyl-2-M^V-dimethylaminopentyl methacrylate] AIBN Benzene
- 202 - 202 - 202 - 202 - 202
- 193 - 256.8 -158.9 - 177.0 - 194.0
55 40-85 RT -75 -75 -78
-96.9
60
42.0
48.9 (MC)
-42(La] 546 )
-41 (M) ([a]
546)
60
-24.4(La] 546 )
-36(MC)(La] 546 )
60
-23.0
- 26.0 (MC)
65
12.1
35 -65 -60 35
- 79,5 -72.5 -100
60
7(M) -151 -138 -190 -147
- 54.4 (M) - 54.4 (M) - 54.4 (M)
5.93 6.84
100 RT 2.2
(M) (M) (M) (M) (M)
- 103 (M) - 103 (M) - 103 (M) -78.8(M) 6.99 (M) 6.99 (M)
-2.1 (M)
Benzene
25
205
120
References page VII-739
TABLE 1.
cont'd
Polymer Catalyst or initiator
Polymerization system Solvent
PoIyK' + )phenyl-2-pyridyl-0-tolylmethyl methacrylate] /t-BuLi THF Diisopropyl peroxydicarbonate
Polymer (P) values
Toluene
Monomer (M) or model compound (MC) values
[M]D -78 40
395 -321 -617([aJ 365 )
[Ml0
Solvent
2T( 0 C)
Refs.
Benzene (M); THF (P) THF Chloroform(M); 90% chloroform-10% TFEL (P)
- 78 (P); 25 (M) 25 (P) 25
223
Chloroform (P); benzene (M) Chloroform (after heating at 600C) Chloroform (P); benzene (M) Chloroform (after heating at 600C)
25 25
224
25 25
224
- 47.6 (M) -47.6(M)
Chloroform Chloroform
25 25
121
- 37.7 (M) - 37.7 (M)
Chloroform Chloroform
25
121
-99.7 (M)
Chloroform
88.6 (M) 190.1 (M)(M 365 )
PoIvK + )phenYl-2-pyridyl-m-tolYlmethyl methacrylate I DPEDA-Li/(- )DDB Toluene
-78
-845(La] 365 ) 1481 (La] 365 )
14.0(M)(LaJ 3 6 5 )
DPEDA-Li/TMEDA
-78
262(LaJ 365 ) 1370(La] 365 )
14.0(M)(La] 365 )
Toluene
Optical activity measured
185
1.4. POLY(VINYL ETHERS), POLY(VINYL KETONES), POLY(VINYL ESTERS) 1.4.1. POLY(VINYL ETHERS) PoIyK- )(5)2,2/-bis(2-vinyloxyethoxy)-l,l/-binaphthyl] DCM 0 -131.6 SnCl4 Nitromethane 0 -131.9 BF 3 OEt 2 PoIyK- )(5)2,2/-bisl2-(2-vinyIoxyethoxy)ethoxy]-l ,1 '-binaphthylj -93.9 SnCl4 DCM O -95.8 BF 3 OEt 2 DCM O PoIyK-)(5)2,2 / -bisL2-(2-vinyloxyethoxy)ethoxy]-3,3 / ~dimethyl-l,r-binaphthyl] DCM O SnCl4 44.5 Poly( 1 -bornyloxyethylene) BF 3 OEt 2 PoIy(I -cholesteryloxyethylene) Poly( 1,2: 5,6-diisopropylidene-a-D-glucofuranosyl-3-oxyethylene) BF3 OEt2 n-Hexane + DCM -78 Poly( 1 -menthyloxyethylene) C 4 H 9 MgBr Toluene 80 BF 3 OEt 2 M-Hexane -78 SnCl4 Petroleum ether 25 Mn-MoO 3 -H 2 SO 4 /i-Hexane -10 Mn-MoO 3 -H 2 SO 4 Az-Hexane -30 A1(/-OC 3 H 7 ) 3 /H 2 SO 4 rc-Pentane - 15 to RT -198 BF 3 OEt 2 Toluene -78 -220 Poly( 1 -a-methy lbenzyloxyethylene) BF 3 OEt 2 Propane -78 Polyt(S)2-methylbutyloxyethylene] Al(Z-C 4 H 9 )Cl 2 Propylene + Toluene -78
25 25 (P); 29 (M) -142 -93
-122.4(M) - 131.4 (M)
5.7
-77.2
-358 -396 -373 -357 -353
- 121.9(M) -121.9(M) -121.9(M) - 118.8(M) - 118.8(M) - 72.2 (M) -61.5 (M)
68.6
-71.9 (M)
4.9
1.1 (MC) 7.6 (M) 1.1 (MC) 7.6 (M) 1.1 (MC) 7.6 (M)
A1(/-C 4 H 9 ) 3 /H 2 SO 4
Ether
15-20
-5.9
A1(/-OC 3 H 7 ) 3 /H 2 SO 4
Ethyl acetate
0-20
6.4
Benzene
245
25
31 31
EDC (P); ethanol (M)
25
36,24
Benzene (P); chloroform (M) Benzene (P) Benzene (P) Chloroform (M); benzene (P) Benzene (P) Neat (M); benzene (P) Toluene (M); benzene (P)
25 25 25 25 25 25 25 (P)
Benzene
25
35
Toluene (P); neat (M1MC)
25
34
Toluene (P)
25
Toluene (P)
25
31 33 123 124
Po Iy [(S) 1 -methylpropyloxyethylenej Al(Z-C 4 H 9 )Cl 2 Propylene -f Toluene -78 AI(Z-C 4 H 9 )SZH 2 SO 4 15-20 Diethyl ether Al(Z-OC 3 H 7 ) 3/H 2 SO 4 - 15 to RT rc-Pentane Polyl(S)2-phenylvinyl 2-methylbutyl ether] -78 BF 3 OEt 2 Toluene -78 SnCl4 Toluene Poly[(S)2-phenylvinyl 3-methylpentyl ether] BF 3 OEt 2 -78 Toluene SnCl4 Toluene -78 1.4.2. POLY(VINYL KETONES) Poly[(5)2-methylbutyl vinyl ketone] Spontaneous LiAlH 4 Toluene Poly[(S)3-methylpentyl vinyl ketone] Spontaneous Toluene LiAlH 4 Poly[(S) 1 -methylpropyl vinyl ketone] LiAlH4 Toluene Spontaneous Toluene AIBN Toluene LiAlH4 1.4.3. POLY(VINYL ESTERS) Poly(-acetyl)L-serine methylester)methylenej NiCl 0 -6H 2 O Chloroform
-190([M] 578 )
58.3 ([OCj 578)
74.0(M) ([MJ 57 S).
Chloroform
20-22
132
- i l l ([a].™) -172([M] 578 )
46.8 ([(X]578)
72.5 (M) [[M]5n)
Chloroform
20-22
132
-129 (M) ([M] 578 )
Chloroform
20-22
132
-58.1 (M)
Chloroform-methanol (5 :2) (P); chloroform (M)
20
231
-12.0(M)
Chloroform-methanol
20
231
40.6 (La] 578)
Chloroform
22
249
18.6 ([a]578)
Chloroform
22
249
-13.5(M)
Chloroform-methanol (5:2) (P); chloroform (M)
20
230
-82(IaJ 5 7 8 ) 205
Poly[(L-alanyl-(O-acetyl)D-serine methylester)methylenej -33 NiCl 2 -6H 2 O Chloroform Poly[(L-alanyl-(Af(Im)-tosyl)L-histidine methylester)methylenej NiCl 2 -6H 2 O Chloroform/Methanol RT 144(Ia] 578 ) Poly[(D-alanyl-(Ar(Im)-tosyl)L-histidine methylester)methylenej NiCl 2-6H 2 O Chloroform/Methanol RT -170 (N 578 ) Poly[(L-alanyl-(/V(Im)~tosyl) L-histidyl-(O-acetyl)L-serine methylester)methylenej -58.9 NiCl 2 6H 2 O Chloroform
-156([M] 5 7 8 )
-68.5
([a]578)
Poly[(L-alanyl-(A^(Im)-tosyl)L-histidyl-(O-acetyl)D-serine methylester)methylene] NiCl 2 6H2O Chloroform - 29.3 Poly[(D-alanyl-(Af(Im)4osyl)L-histidyl-(0-acetyl)L-serine methylester)methylene] NiCl 2 6H 2 O Chloroform -8.0 Poly [ ((S)( 1 -benzylethyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 15 (La] 578 ) PolyL(((5)l-(ferf-butoxycarbonyl)-2-methylpropyl)imino)methylene] NiCl 2 45 32.5 Poly[((S)( 1 -carbethoxyethyl)imino)methylene] NiCl 2 6H 2 O RT -280(La] 5 7 8 ) Poly [(((1S ,2S) 1 -carbomethoxy-2-methylbutyl)imino)methy lene] NiCl 2 45 -32.2 Poly[((S)(— )a-cyclohexylethylimirio)methylene] NiCl 2 -6H 2 O Neat 65 -295 Poly[(((S)2,2-dimethyl-13-dioxolane-4-yl)methylimino)methylene] NiCl 2 6H 2 O RT 68.5(La] 546 ) Poly [(((R) 1,2-dimethylpropyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 16.7(La] 578 ) Poly[((/?)(2-(diphenyl phosphinyl)propyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -338(La] 578 ) PoIyK(SX 1 -ethyl-2-propenyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT 29(La] 578 ) PoIyK(SX 1 -ethyl-2-propynyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -HO(La] 5 7 8 ) PolyL(((S)l-(isopropyloxycarbonyl)-2-methylpropyl)imino)methylene] NiCI 2 5 -24 Poly[((-)menthylimino)methyleneJ NiCl 2 -6H 2 O Methanol 65 -207 Poly [(((S) 1 -(methoxycarbonyl)-2-methylpropyl)imino)methylene] NiCl2 RT -UO Poly[((/?)3-methyl-2-butyl)imino)methylene] NiCl 2 -6H 2 O Methanol RT -16.7 ([a]578) Poly[((i?)4-methyl-2-pentyl)imino)methylene] NiCl 2 6H2O RT 62([aJ 578 ) Poly[((/?)2-octylimino)methylene] NiCl 2 -6H 2 O Methanol RT 34 (M 578 ) Poly[(d-a-phenylethylimino)methylene] DBP-O2 Heptane 60 365 Poly[(l-a-phenylethylimino)methylene] H 2 SO 4 -O 2 Heptane 50 -382 NiCl 2 -6H 2 O 0-5 -350 (M 578 )
20
230
Chloroform-methanol (5:2) (P); chloroform (M)
20
230
Chloroform
20-22
132
Chloroform
20
236
Chloroform
20-22
132
Chloroform
20
236
THF (P); hexane (MC)
24 (P); 20 (MC) 209
38.5(M)(La] 5 4 6 )
Dioxane
25
227
-24.2 (M) (La) 578 )
Chloroform
22
236
(M)
9.2 (M)
22(LM] 5 7 8 )
48.7(LaJ 5 7 8 )
70.6(M)(LM] 5 7 8 )
29.5 (M) -355([M] 578 )
16.7 (LaJ 578 )
21.2(M)(LM] 5 7 8 )
35.0 (M) 27.4 (MC)
-910([M] 578 )
13.1 (La]578)
35.3 (M) ([M]578)
Chloroform
20-22
132
27.6(LM] 578 )
95 (La] 578 )
90.2 (M) ([M]578)
Chloroform (P); neat (M)
20
132
-102(LM] 5 7 8 ) -12.8 ([a]578)- 11.9(M)(LM] 5 7 8 )
Chloroform (P); neat (M)
20-22
132
Chloroform
20
236
Hexane
25 (P); 20 (MC) 209
Chloroform
20
236
- 16.2 (LM] 578 ) -24.2(La] 578 )- 23.5(M)(LM] 5 7 8 )
Chloroform
22
131
68.9([MJ 578 )
-61.9 (La] 578 )- 68.8(M)(LM] 578 )
Chloroform
22
131
47.3 ([M]578)
-47.6
Chloroform
22
131
Toluene
27
39
Toluene Chloroform (P); methanol (M)
27 20
39 132
n-Heptane (P); neat (MC)
25
133
-68.8(M)
Chloroform
20
197
5.90 (M)
Chloroform
20
197
32.7 (M) - 106.4 (MC) 5.5 (M)
(La] 578 )- 66.3(M)(LM] 5 7 8 )
37.2 (M)
-458([M] 578 )
- 35.8 (M) -40.9
-179.7(M) 55.0(M)(LM] 578 )
POLY(ALKYNES)
Poly[(S)3,4-dimethyl-1 -pentyne] Al(Z-C 4 H 9 ) 3/Fe(AcAc) 3 n-Heptane Poly [p-(L-( - )-menthoxycarbonyl)phenylacety lene] [Rh(norbornadiene)Cl] 2 Triethylamine Poly [/?-((-f )-2-methylbutoxy)phenylacetylene] [Rh(norbornadiene)Cl] 2 Triethylamine
20-35 RT RT
42.2 (MC)
470 -605 19.2
6££-IIA 3^d S90U3J9J9H
1.8.
Chloroform -methanol (5 :2) (P); chloroform (M)
-2.1
TABLE 1. cont'd Polymer Catalyst or initiator Poly [(S)4-methyl-1 -hexyne] Al(Z-C 4 H 9 ) 3/Fe(AcAc) 3 AlO-C 4 H 9 ) 3/Fe(AcAc) 3 Poly[(S)5-methyl-1 -heptyne] Al(I-C 4 Hg) 3 ZFe(AcAc) 3 Poly[(5)6-methyl-1 -octynej Al(i-C 4 H 9 ) 3 ZFe(AcAc)3 Poly [(S)3-methyl-1 -pentynej Al(Z-C 4 H 9) 3/Fe(AcAc) 3
Polymerization system Solvent
T(0C)
Isooctane w-Heptane
20-30 20-35
^-Heptane
Polymer (P) values WD
[M] D
Monomer (M) or model compound (MC) values MD
[M]D
Optical activity measured Solvent
T( 0 C)
Refs.
-10.6
- 3.0 (MC)
Isooctane >2-Heptane (P); neat (MC)
25 25
133
20-35
-146
12.2(MC)
n-Heptane (P); neat (MC)
25
133
n- Heptane
20-35
-34
13.7(MC)
rc-Heptane (P); neat (MC)
25
133
/7-Heptane
20-35
498
32.1 (MC)
/i-Heptane (P); neat (MC)
25
133
THF (P); ethanol (M) THF (P) THF (P)
25(P) 25(P) 25(P)
-2.97 (MC)
-22.9
1.9. POLY(MALEIMIDES) AND RELATED POLYMERS Poly(AMx>myl maleimide) BPO THF 50 AIBN THF 50 n-BuLi THF 50 Poly[A^(cholesteroxycarbonylmethyl)maleimide] AIBN THF 70 «-BuLi THF 0 Poly(/V-maleoyl-L-alanine) AIBN THF 60 Poly(/V-maleoyl-L-phenylalanine) AIBN THF 60 Poly[7V-maleoyl-L-phenylalanine ethyl esterj AIBN Dioxane 60 BuLi THF 0 Poly[Ar-((N/-((Z?)-a-methylbenzyl)aminocarbonyl)methyl)maleimideJ AIBN DCM 70 Polyt/V^./V'^^-a-methylbenzyOaminocarbonyl-fz-pentyl) maleimide] AIBN Dioxane 60 Poly[Ar-(4^/-((/?)-a-methylbenzyl)aminocarbonylphenyl)maleimideJ AIBN THF 50 rc-BuLi THF 0 Poly[A^-(4-A^'-((5)-a-methylbenzyl)aminocarbonylpheny))ma]eimideJ AIBN THF 50 Poly[W6 O-anhydro^^^-tri-O-benzyl-p-D-galactopyranose] PF5 DCM -78 Polyfoc-1,6-anhydro-2,3,4-tri-
