Organic reactions catalyzed by copper(I) hydride complexes

Chapter 2. Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes A chemoselective hydrometalation process enables the use of easily accessible allenes as allylmetal nucleophile surrogates in imine allylation reactions. By modulating the nitrogen-protecting group, either highly branched- or linear-selective addition can be achieved from the same allene. Both reactions exhibit excellent diastereoselectivity and broad functional-group tolerance. Good enantioselectivity can also be achieved in the linear-selective reaction. Finally, a mechanistic model for the regiodivergence is proposed on the basis of density functional theory calculations. Chapter 3. Enantioselective Ketone Allylation Using Allene, a Petroleum Cracking Byproduct Allene gas is produced and separated on million-metric-ton scale per year during petroleum refining but is rarely employed in organic synthesis.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2019

Author dc:creator

• Liu, Richard Y.(Richard Yifan)

Advisor dc:contributor.advisor

• Stephen L. Buchwald.

• Chemistry.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

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

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/124110

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/124110