Catalytic Enantioselective Formations of C–B, C–C and C–Si Bonds by Organic Molecules or Transition-Metal Complexes

• Main Author: Wu, Hao
• Format: Others
• Language: English
• Published: Boston College 2015
• Subjects: allenyl addition; boryl conjugate addition; copper catalyst; metal free catalyst; N-heterocyclic carbene; silyl conjugate addition
• Online Access: http://hdl.handle.net/2345/bc-ir:104759

Thesis advisor: Amir H. Hoveyda === Catalytic enantioselective reactions are of great importance in synthetic organic chemistry. Thus, development of efficient, selective and easily accessible catalyst for various bond formations is the main task in our laboratories. First, we have developed the first broadly applicable enantioselective boryl conjugate addition reactions to a variety of α,β-unsaturated carbonyls, promoted by a chiral Lewis basic N-heterocyclic carbene. The valuable β-boryl carbonyls were further used in complex molecule syntheses. The mechanism of these C–B bond formations was studied in details. We have also developed a practical method for enantioselective addition of an allene unit to aryl-, heteroaryl- and alkyl-substituted Boc-aldimines. These efficient C–C bond formations, catalyzed by an aminophenol-derived boron-based catalyst, were further utilized in succinct syntheses of anisomycin and epi-cytoxazone. Finally, chiral NHC–Cu complexes were employed for site-, diastereo- and enantioselective silyl conjugate additions to acyclic and cyclic dienones and dienoates. The precious enantiomerically enriched allylsilane obtained can be converted into a ketone-aldol type product, which is difficult to access through alternative methods. === Thesis (PhD) — Boston College, 2015. === Submitted to: Boston College. Graduate School of Arts and Sciences. === Discipline: Chemistry.