Organocatalytic living ring-opening polymerization of cyclic carbosiloxanes

被引：101

作者：

Lohmeijer, Bas G. G.

Dubois, Geraud

Leibfarth, Frank

Pratt, Russell C.

Nederberg, Fredrik

Nelson, Alshakim

Waymouth, Robert M.

Wade, Charles

Hedrick, James L.

机构：

[1] IBM Corp, Almaden Res Ctr, San Jose, CA 95123 USA

[2] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

ORGANIC LETTERS | 2006年 / 8卷 / 21期

关键词：

D O I：

10.1021/ol0614166

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An organocatalytic route to narrowly dispersed poly(carbosiloxanes) of predictable molecular weight and end group fidelity is described. N-Heterocyclic carbenes (NHC) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyze the ring opening of cyclic carbosiloxanes. The pK(b) of the catalyst is important in preventing adverse transetherification reactions and obtaining well-defined polymers. Mechanistic studies indicate that hydrogen bonding to TBD or the NHC activates alcohols or silanols for ring-opening reactions.

引用

收藏

页码：4683 / 4686

页数：4

相关论文

共 34 条

[1] GUANIDINIUM CATALYZED CONJUGATE ADDITION OF PYRROLIDINE TO UNSATURATED LACTONES [J].

ALCAZAR, V ;

MORAN, JR ;

DEMENDOZA, J .

TETRAHEDRON LETTERS, 1995, 36 (22) :3941-3944

[2] Looking for stable carbenes: The difficulty in starting anew [J].

Arduengo, AJ .

ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (11) :913-921

[3] A BIS(CARBENE) PROTON COMPLEX - STRUCTURE OF A C-H-C HYDROGEN-BOND [J].

ARDUENGO, AJ ;

GAMPER, SF ;

TAMM, M ;

CALABRESE, JC ;

DAVIDSON, F ;

CRAIG, HA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (01) :572-573

[4] Stable carbenes [J].

Bourissou, D ;

Guerret, O ;

Gabbaï, FP ;

Bertrand, G .

CHEMICAL REVIEWS, 2000, 100 (01) :39-91

[5] ON THE MECHANISM OF THIAMINE ACTION .4. EVIDENCE FROM STUDIES ON MODEL SYSTEMS [J].

BRESLOW, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (14) :3719-3726

[6] Catalytic generation of activated carboxylates:: Direct, stereoselective synthesis of β-hydroxyesters from epoxyaldehydes [J].

Chow, KYK ;

Bode, JW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (26) :8126-8127

[7] First example of N-heterocyclic carbenes as catalysts for living polymerization:: Organocatalytic ring-opening polymerization of cyclic esters [J].

Connor, EF ;

Nyce, GW ;

Myers, M ;

Möck, A ;

Hedrick, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (06) :914-915

[8] Enantioselective synthesis of α-amino nitriles from N-benzhydryl imines and HCN with a chiral bicyclic guanidine as catalyst [J].

Corey, EJ ;

Grogan, MJ .

ORGANIC LETTERS, 1999, 1 (01) :157-160

[9] Latent, thermally activated organic catalysts for the on-demand living polymerization of lactide [J].

Coulembier, O ;

Dove, AP ;

Pratt, RC ;

Sentman, AC ;

Culkin, DA ;

Mespouille, L ;

Dubois, P ;

Waymouth, RM ;

Hedrick, JL .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (31) :4964-4968

[10]

Cowan JA, 2002, ANGEW CHEM INT EDIT, V41, P1432, DOI 10.1002/1521-3773(20020415)41:8<1432::AID-ANIE1432>3.0.CO

← 1 2 3 4 →