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Halocyclizations and cycloisomerizat...

Strom, Kyle Robert.

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Halocyclizations and cycloisomerizations of 1,6-diynes, and sequence-defined, self-replicating polymers.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Halocyclizations and cycloisomerizations of 1,6-diynes, and sequence-defined, self-replicating polymers./
Author:	Strom, Kyle Robert.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2017,
Description:	275 p.
Notes:	Source: Dissertations Abstracts International, Volume: 78-09, Section: B.
Contained By:	Dissertations Abstracts International78-09B.
Subject:	Organic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10196511
ISBN:	9781369654578

Halocyclizations and cycloisomerizations of 1,6-diynes, and sequence-defined, self-replicating polymers.
Strom, Kyle Robert.

Halocyclizations and cycloisomerizations of 1,6-diynes, and sequence-defined, self-replicating polymers. - Ann Arbor : ProQuest Dissertations & Theses, 2017 - 275 p.

Source: Dissertations Abstracts International, Volume: 78-09, Section: B.

Thesis (Ph.D.)--Boston University, 2017.

This item must not be added to any third party search indexes.

The exploration of chemical space in search of molecules that perturb or mimic biological systems is essential to understanding human biology. The first part of this dissertation (Chapters 1-4) describes efforts to aid in the exploration of biologically relevant space through the invention of new π-cyclization methodologies. This strategy can be viewed as part of a "top-down" approach to investigating biology: the construction of small molecule drugs or probes which modify the behavior of the existing system. The second part of this dissertation (Chapter 5) describes preliminary efforts to expand life-like chemical space beyond the nucleic acids of DNA and RNA. This can be viewed as a "bottom-up" approach to biology: the construction of systems which mimic the features of biochemical processes. In part one, cyclizations of nitrogen tethered 1,6-diynes were developed as a means to new heterocyclic scaffolds. A GaX3 promoted halocyclization transformed the acyclic diynes into tetrahydropyridine rings with exocyclic vinyl halides. In the presence of strong acid, the tetrahydropyridine products were further cyclized to tetrahydroindenopyridine scaffolds. These scaffolds were then diversified through Pd(0)-catalyzed cross-coupling reactions of the vinyl halide, and modifications to the tethering amino nitrogen. Subsequently, a Bronsted acid-catalyzed cyclization was developed, transforming N-sufonyl tethered bis-aryl 1,6-diynes to dihydroindenopyridines. Using unsymmetric bis-aryl diynes, the regio- and chemoselectivity of this Bronsted acid-catalyzed cyclization was investigated, and compared to the GaX3 Lewis acid promoted cyclization developed previously. The regiochemical preference of the initial cyclization step was found to be reversed under the two different conditions. In part two, a means to sequence-defined synthetic polymers which emulate the information storage and self-replication abilities of nucleic acid-based biopolymers was designed. Information was encoded in two dimers as a specific sequence of aniline and benzaldehyde subunits, which were linked together by a diethynyl benzene backbone. These dimers functioned as a template for the synthesis of new dimers with a complementary sequence. Unpolymerized ethynylaniline and ethynylbenzaldehyde monomers, associated to a polymer template by reversible imine bonds, were polymerized via Sonogashira cross coupling with diiodobenzene. Under the same set of conditions, the sequence of two parent dimers was transferred to the daughters.

ISBN: 9781369654578Subjects--Topical Terms:

523952
Organic chemistry.

Halocyclizations and cycloisomerizations of 1,6-diynes, and sequence-defined, self-replicating polymers.
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500 $a Source: Dissertations Abstracts International, Volume: 78-09, Section: B.
500 $a Publisher info.: Dissertation/Thesis.
500 $a Advisor: Snyder, John K.
502 $a Thesis (Ph.D.)--Boston University, 2017.
506 $a This item must not be added to any third party search indexes.
506 $a This item must not be sold to any third party vendors.
520 $a The exploration of chemical space in search of molecules that perturb or mimic biological systems is essential to understanding human biology. The first part of this dissertation (Chapters 1-4) describes efforts to aid in the exploration of biologically relevant space through the invention of new π-cyclization methodologies. This strategy can be viewed as part of a "top-down" approach to investigating biology: the construction of small molecule drugs or probes which modify the behavior of the existing system. The second part of this dissertation (Chapter 5) describes preliminary efforts to expand life-like chemical space beyond the nucleic acids of DNA and RNA. This can be viewed as a "bottom-up" approach to biology: the construction of systems which mimic the features of biochemical processes. In part one, cyclizations of nitrogen tethered 1,6-diynes were developed as a means to new heterocyclic scaffolds. A GaX3 promoted halocyclization transformed the acyclic diynes into tetrahydropyridine rings with exocyclic vinyl halides. In the presence of strong acid, the tetrahydropyridine products were further cyclized to tetrahydroindenopyridine scaffolds. These scaffolds were then diversified through Pd(0)-catalyzed cross-coupling reactions of the vinyl halide, and modifications to the tethering amino nitrogen. Subsequently, a Bronsted acid-catalyzed cyclization was developed, transforming N-sufonyl tethered bis-aryl 1,6-diynes to dihydroindenopyridines. Using unsymmetric bis-aryl diynes, the regio- and chemoselectivity of this Bronsted acid-catalyzed cyclization was investigated, and compared to the GaX3 Lewis acid promoted cyclization developed previously. The regiochemical preference of the initial cyclization step was found to be reversed under the two different conditions. In part two, a means to sequence-defined synthetic polymers which emulate the information storage and self-replication abilities of nucleic acid-based biopolymers was designed. Information was encoded in two dimers as a specific sequence of aniline and benzaldehyde subunits, which were linked together by a diethynyl benzene backbone. These dimers functioned as a template for the synthesis of new dimers with a complementary sequence. Unpolymerized ethynylaniline and ethynylbenzaldehyde monomers, associated to a polymer template by reversible imine bonds, were polymerized via Sonogashira cross coupling with diiodobenzene. Under the same set of conditions, the sequence of two parent dimers was transferred to the daughters.
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