Dissertation/Thesis Abstract

Design and Development of New Aerobic Boron Heck Reactions
by McAlpine, Neil James, Ph.D., Princeton University, 2018, 124; 10977124
Abstract (Summary)

Transition-metal catalyzed cross-coupling has, in many ways, revolutionized synthetic chemistry by providing streamlined syntheses using highly modular building blocks. Despite the widespread application of the Suzuki and Buchwald-Hartwig cross-coupling reactions, utilization of more contemporary cross-coupling protocols is narrower. Progress in applied research using transition- metal catalyzed reactions is often hampered by the necessity for unwieldy substrate syntheses. Seeking to tackle this problem, we have developed two novel C-C bond forming reactions in the context of the oxidative boron Heck reaction that converts simple starting materials into highly useful products which are directly applicable to many powerful synthetic protocols.

Firstly, an aerobic boron Heck reaction has been developed, which facilitates the conversion of feedstock olefins, namely, ethylene and propylene to styrenes and b-methylstyrenes using abundant (hetero)aryl boronic acids. The relevance to complex molecule synthesis is highlighted by a two-step synthesis of the pharmaceutical phenprocoumon.

Secondly, an aerobic boron Heck reaction of cyclobutene has been developed using abundant (hetero)aryl boronic acids. Instead of forming the classical Heck product (3-aryl-cyclobutene) a linear 1-aryl-1,3-diene is generated with complete chemo-, regio- and stereo-selectivity. 1-Aryl- 1,3-dienes have found myriad applications in modern transition-metal catalyzed cross-couplings however the substrates are often prepared by poorly efficient Wittig reactions. Both computational and mechanistic experimental data support a mechanism that proceeds by a classical Heck reaction followed by pericyclic ring opening mechanism for C-C bond cleavage. 1-Aryl-1,3,5-trienes were similarly prepared using alkenyl boronic acids.

Indexing (document details)
Advisor: Carrow, Brad P.
Commitee: Schwartz, Jeffrey, Semmelhack, Martin
School: Princeton University
Department: Chemistry
School Location: United States -- New Jersey
Source: DAI-B 80/04(E), Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Organic chemistry
Keywords: Alkenyl boronic acids, Cross-coupling reactions, Pericyclic ring opening
Publication Number: 10977124
ISBN: 9780438738034
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