The synthesis of sterically demanding ligands and examples of their copper complexes

Conditions for promoting the Pd-catalyzed arylation of (N-pyrrolyl)zinc derivatives have been established using aryl bromides, chlorides, and iodides as substrates. In most cases, 0.5 mol% Pd(OAc)₂ can achieve the desired transformation in roughly 24 hours, with the more sterically demanding substrates requiring altered conditions. Typical isolated yields are in excess of 70%. Moreover, methyl- and aryl-substituted pyrrolyl anions have been shown to display similar chemistry using 5.0 mol% Pd(OAc)₂. Though they require longer reaction times, the isolated yields rival those of the unsubstituted analogs. Two new copper(I) N-heterocyclic carbene complexes containing the 2,4,6,2",4",6"-hexaisopropyl-1,1':3',1"-terphenyl moiety have been synthesized and isolated. The LCuCl complex (92% isolated yield) was made via a one-pot synthesis from the corresponding imidazolinium tetrafluoroborate salt, NaH, and CuCl (L = [1,3-bis-(2,4,6,2",4",6"-hexaisopropyl- [1,1':3',1"]terphenyl-5'-yl)-4,5-dihydroimidazol-2-ylidene]). The LCuOAc complex (71% isolated yield) was made the same way using CuOAc in place of CuCl.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2004

Author dc:creator

• Rieth, Ryan D., 1978-

Advisor dc:contributor.advisor

• Joseph Sadighi.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

en_US

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/28703

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/28703