220 Macromolecules, Vol. 43, No. 1, 2010
Matson and Grubbs
4.00-4.20 (br s, 2n H), 3.58-3.65 (m, 2H), 5.40-5.80 (d, 2n H),
7.20-7.45 (m, 5H). GPC: Mn = 7100, Mw/Mn = 1.08.
P(tBENI)dCHCH2CH2CH2Br by CM (36). 1H NMR: δ
1.20-1.80 (m, 10n H), 2.00-2.30 (m, n H), 2.70-3.40 (m, 4n
H), 3.42-3.52 (m, 2H), 4.00-4.20 (br s, 2n H), 5.40-5.80 (d, 2n
H), 7.20-7.45 (m, 5H). GPC: Mn = 7600, Mw/Mn = 1.03.
P(tBENI)dCHCH2CH2CH2SAc by CM (37). To minimize
overlapping peaks in the NMR spectrum, the tert-butyl
ester group was removed by treatment with trifluoroacetic
acid as in polymer 29. The product was characterized as
P(CMNI)dCHCH2CH2CH2SAc. 1H NMR (DMSO-d6): δ
1.40-1.60 (s, n H), 1.90-2.05 (s, n H), 2.32 (s, 3H) 2.60-2.70
(s, n H), 2.82 (m, 2H), 2.90-3.10 (m, 3n H), 3.90-4.05 (s, 2n H),
5.35-5.70 (m, 2n H), 6.88 (m, 2H), 7.13 (m, 2H), 7.18-7.42 (m,
5H), 12.80-13.20 (s, n H). GPC was not performed due to low
solubility in THF.
(7) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18–29.
(8) For recent reviews see: Lo Verso, F.; Likos, C. N. Polymer 2008,
49, 1425–1434. Hadjichristidis, N.; Pitsikalis, M.; Pispas, S.; Iatrou, H.
Chem. Rev. 2001, 101, 3747–3792. Hatada, K.; Kitayama, T. Polym.
Int. 2000, 49, 11–47. For a review on end-capping of ROMP polymers
see: Hilf, S.; Kilbinger, A. F. M. Nat. Chem. 2009, 1, 537–546.
(9) Yagci, Y.; Tasdelen, M. A. Prog. Polym. Sci. 2006, 31, 1133–1170.
(10) (a) Chen, B.; Metera, K.; Sleiman, H. F. Macromolecules 2005, 38,
1084–1090. (b) Boyer, C.; Liu, J.; Bulmus, V.; Davis, T. P.;
Barner-Kowollik, C.; Stenzel, M. H. Macromolecules 2008, 41,
5641–5650.
(11) (a) Laurent, B. A.; Grayson, S. A. J. Am. Chem. Soc. 2006, 128,
4238–4239. (b) Eugene, D. M.; Grayson, S. M. Macromolecules 2008,
41, 5082–5084. (c) Adachi, K.; Honda, S.; Hayaski, S.; Tezuka, Y.
Macromolecules 2008, 41, 7898–7903. (d) Lepoittevin, B.; Dourges,
M. A.; Masure, M.; Hemery, P.; Baran, K.; Cramail, H. Macromole-
cules 2000, 33, 8218–8224.
(12) (a) Amass, A. J.; Bas, S.; Gregory, D.; Mathew, M. C. Makromol.
Chem. 1985, 186, 325–330. (b) Castle, T. C.; Hutchings, L. R.;
Khosravi, E. Macromolecules 2004, 37, 2035–2040. (c) Tritto, I.;
Sacchi, M. C.; Grubbs, R. H. J. Mol. Catal. 1993, 82, 103–111. (d)
Coca, S.; Paik, H. J.; Matyjaszewski, K. Macromolecules 1997, 30,
6513–6516. (e) Li, M. H.; Keller, P.; Albouy, P. A. Macromolecules
2003, 36, 2284–2292. (f) Matson, J. B.; Grubbs, R. H. Macromolecules
2008, 41, 5626–5631.
P(tBENI)dCHCH2O-p-CH2CH2NHBoc-C6H4 by CM (38).
1H NMR: δ 1.20-1.80 (m, 10n H), 2.00-2.30 (m, n H),
2.70-3.40 (m, 4n H), 4.00-4.20 (br s, 2n H), 5.40-5.80 (d, 2n
H), 6.91-6.96 (m, 2H), 7.20-7.45 (m, 5H), 7.12-7.17 (m, 2H).
GPC: Mn = 6900, Mw/Mn = 1.04.
P(tBENI)dCHCH2O-p-CH2CH2NHbiotin-C6H4 by CM
(39). 1H NMR (DMSO-d6):
δ 1.20-1.80 (m, 10n H),
(13) Burtscher, D.; Saf, R.; Slugovc, C. J. Polym. Sci., Part A: Polym.
Chem. 2006, 44, 6136–6145.
(14) Hilf, S.; Kilbinger, A. F. M. Macromol. Rapid Commun. 2007, 28,
1225–1230.
2.00-2.30 (m, n H), 2.70-3.40 (m, 4n H), 4.00-4.20 (br s, 2n
H), 4.27 (t, J = 3.6 Hz, 1H), 4.45 (s, 2H), 5.40-5.80 (d, 2n H),
6.31 (s, 1H), 6.38 (s, 1H), 6.82 (m, 2H), 7.07 (m, 2H), 7.20-7.45
(m, 5H), 7.78 (s, 1H). GPC: Mn = 8000, Mw/Mn = 1.02.
P(tBENI)dCHCH2O-p-CH2CH2NHFITC-C6H4 by CM
(15) (a) Cramail, H.; Fontanille, M.; Soum, A. J. Mol. Catal. 1991, 65,
193–203. (b) Chung, T. C.; Chasmawala, M. Macromolecules 1991,
24, 3718–3720. (c) France, M. B.; Grubbs, R. H.; McGrath, D. V.;
Paciello, R. A. Macromolecules 1993, 26, 4742–4747. (d) Hillmyer,
M. A.; Grubbs, R. H. Macromolecules 1993, 26, 872–874. (e) Maughon,
B. R.; Morita, T.; Bielawski, C. W.; Grubbs, R. H. Macromolecules 2000,
33, 1929–1935.
(16) (a) Katayama, H.; Urushima, H.; Ozawa, F. J. Organomet. Chem.
2000, 1, 16–25. (b) Bielawski, C. W.; Louie, J.; Grubbs, R. H. J. Am.
Chem. Soc. 2000, 122, 12872–12873. (c) Ambade, A. V.; Yang, S. K.;
Weck, M. Angew. Chem., Int. Ed. 2009, 48, 2894–2898.
(17) (a) Katayama, H.; Fukuse, Y.; Nobuto, Y.; Akamatsu, K.; Ozawa,
F. Macromolecules 2003, 36, 7020–7026. (b) Owen, R. M.; Gestwicki,
J. E.; Young, T.; Kiessling, L. L. Org. Lett. 2002, 4, 2293–2296. (c)
Kolonko, E. M.; Kiessling, L. L. J. Am. Chem. Soc. 2008, 130, 5626–
5627.
(40). 1H NMR (DMSO-d6):
δ 1.20-1.80 (m, 10n H),
1.90-2.10 (m, n H), 2.60-3.40 (m, 4n H), 4.00-4.20 (br s, 2n
H), 5.40-5.80 (d, 2n H), 6.48-6.80 (m, 10H), 6.85-7.00
(m, 2H), 7.10-8.30 (m, 8H). Note that because the peaks from
the initiator-derived phenyl end group overlapped with the
peaks of the terminating agent, the value for the end-functionaliza-
tion efficiency in Table 1 was determined by comparing the initial
monomer/catalyst ratio with the integral ratio of the backbone
olefin protons at 5.40-5.80 ppm to the protons derived from the
TA at 6.85-7.00 ppm. GPC: Mn = 10000, Mw/Mn = 1.06.
Acknowledgment. We thank Materia for catalyst as well as
the National Science Foundation (CHE-0809418), the National
Institutes of Health (R01 GM31332), and the National Cancer
Institute (5U54 CA119347) for funding. Yan Xia is acknowl-
edged for a generous donation of TA 7. We also thank Paul G.
Clark and Dr. David VanderVelde for NMR assistance.
(18) Lexer, C.; Saf, R.; Slugovc, C. J. Polym. Sci., Part A: Polym. Chem.
2009, 47, 299–305.
(19) Hilf, S.; Grubbs, R. H.; Kilbinger, A. F. M. J. Am. Chem. Soc.
2008, 130, 11040–11048.
(20) Murphy, J. J.; Kawasaki, T.; Fujiki, M.; Nomura, K. Macromole-
cules 2005, 38, 1075–1083.
(21) (a) Hilf, S.; Berger-Nicoletti, E.; Grubbs, R. H.; Kilbinger, A. F. M.
Angew. Chem., Int. Ed. 2006, 45, 8045–8048. (b) Hilf, S.; Kilbinger,
A. F. M. Macromol. Rapid Commun. 2007, 28, 1225–1230. (c) Hilf,
S.; Hanik, N.; Kilbinger, A. F. M. J. Polym. Sci., Part A: Polym.
Chem. 2008, 46, 2913–2921. (d) Hilf, S.; Kilbinger, A. F. M. Macro-
molecules 2009, 42, 1099–1106.
References and Notes
(1) (a) Grubbs, R. H. Handbook of Metathesis; Wiley-VCH: Weinheim,
2003; Vol. 3. (b) Bielawski, C. W.; Grubbs, R. H. Prog. Polym. Sci.
2007, 32, 1–29.
(2) (a) Bertin, P. A.; Watson, K. J.; Nguyen, S. T. Macromolecules
2004, 37, 8364–8372. (b) South, C. R.; Burd, C.; Weck, M. Acc. Chem.
Res. 2007, 40, 63–74. (c) Kluger, C.; Binder, W. H. J. Polym. Sci., Part
A: Polym. Chem. 2007, 45, 485–499. (d) Matson, J. B.; Grubbs, R. H.
J. Am. Chem. Soc. 2008, 131, 6731–6733. (e) Kolonko, E. M.;
Pontrello, J. K.; Mangold, S. L.; Kiessling, L. L. J. Am. Chem. Soc.
2009, 131, 7327–7333.
(3) (a) Gorodetskaya, I. A.; Choi, T. L.; Grubbs, R. H. J. Am. Chem.
Soc. 2007, 129, 12672–12673. (b) Gorodetskaya, I. A.; Gorodetsky,
A. A.; Vinogradova, E. V.; Grubbs, R. H. Macromolecules 2009, 42,
2895–2898.
(22) Matson, J. B.; Virgil, S. C.; Grubbs, R. H. J. Am. Chem. Soc. 2009,
131, 3355–3362.
(23) (a) Choi, T. L.; Grubbs, R. H. Angew. Chem., Int. Ed. 2003, 42,
1743–1746. (b) Camm, K. D.; Castro, N. M.; Liu, Y.; Czechura, P.;
Snelgrove, J. L.; Fogg, D. E. J. Am. Chem. Soc. 2007, 129, 4168–4169.
(c) Kratz, K.; Breitenkamp, K.; Hule, R.; Pochan, D.; Emrick, T.
Macromolecules 2009, 42, 3227–3229. (d) Colak, S.; Tew, G. N.
Macromolecules 2008, 41, 8436–8440.
(24) Rawat, M.; Gama, C. I.; Matson, J. B.; Hsieh-Wilson, L. C. J. Am.
Chem. Soc. 2008, 130, 2959–2961.
(25) Breitenkamp, R. B.; Ou, Z.; Breitenkamp, K.; Muthukumar, M.;
Emrick, T. Macromolecules 2007, 40, 7617–7624.
ꢀ
(4) (a) Helms, B.; Mynar, J. L.; Hawker, C. J.; Frechet, J. M. J. J. Am.
Chem. Soc. 2004, 126, 15020–15021. (b) Boydston, A. J.; Holcombe,
(26) Eren, T.; Som, A.; Rennie, J. R.; Nelson, C. F.; Urgina, Y.;
Nu€sslein, K.; Coughlin, E. B.; Tew, G. N. Macromol. Chem. Phys.
2008, 209, 516–524.
ꢀ
T. W.; Unruh, D. A.; Frechet, J. M. J.; Grubbs, R. H. J. Am. Chem. Soc.
2009, 131, 5388–5389.
(5) Xia, Y.; Kornfield, J. A.; Grubbs, R. H. Macromolecules 2009, 42,
3761–3766.
(27) Chatterjee, A. K.; Choi, T. L.; Sanders, D. P.; Grubbs, R. H. J. Am.
Chem. Soc. 2003, 125, 11360–11370.
(6) (a) Boydston, A. J.; Xia, Y.; Kornfield, J. A.; Gorodetskaya, I. A.;
Grubbs, R. H. J. Am. Chem. Soc. 2008, 130, 12775–12882. (b) Xia,
Y.; Boydston, A. J.; Yao, Y.; Kornfield, J. A.; Gorodetskaya, I. A.;
Spiess, H. W.; Grubbs, R. H. J. Am. Chem. Soc. 2009, 131, 2670–2677.
(28) Raederstorff, D.; Shu, A. Y. L.; Thompson, J. E.; Djerassi, C.
J. Org. Chem. 1987, 52, 2337–2346.
(29) Dag, A.; Durmaz, H.; Sirkecioglu, O.; Hizal, G.; Tunca, U.
J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 2344–2351.