Frank W. Fowler

Synthetic Chemistry

The problem of converting the materials we have into the materials we want is the domain of synthetic chemistry. Historically, the focus of synthetic chemistry has been on the molecule. Molecular synthesis has rapidly developed and been extremely successful, particularly in medicinal chemistry.

Functional materials with valuable optical, electrical, chemical and physical properties depend not only upon the nature of the constituent molecules but upon their relationship to each other or the supramolecular structure. If the preparation of designed materials is to ever be a rational process, it is necessary to control the molecular as well as the supramolecular structure. The extension of synthetic chemistry from the molecule to large ensembles of molecules, or supramolecular structures, is among the greatest challenges facing contemporary chemistry.

A major goal of our research group is the development of strategies for the preparation of designed materials. This process first requires an understanding of the weak forces involved in the assembly of molecules to design a supra-molecular structure. The next step requires the molecular synthesis of a compound that will assemble into the designed supramolecular structure followed by conditions necessary for the assembly process.

An example of an application of our studies is the preparation of layered polydiacetylenes. Polymers of the diacetylene functionality are interesting materials because their extensively conjugated pi-systems imparts to them useful optical and electrical properties. They are prepared by a process controlled by their solid state structure. We have applied our strategies for preparing layers and organizing molecules for the required topochemical polymerization. The figure below shows the crystal to crystal conversion of a diacetylene to a polydiacetylene.

The preparation of designed materials is a difficult problem requiring a multidisciplinary approach. Participants in this project mustbecome skilled in understanding the weak forces that assemble molecules, instrumental techniques for analyzing the structure of the organic solid state, and modern methods of synthetic chemistry.

A convergent synthetic strategy for the preparation of layered diacetylenes for a topochemically controlled polymerization.

Development of a strategy for the preparation of polydiacetylenes. Curtis SM, Le N, Lauher JW, Fowler FW ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 222: 547-ORGN Part 2 AUG 2001

The host guest co-crystal approach to supramolecular structure Kane JJ, Nguyen T, Xiao J, Fowler FW, Lauher JW MOLECULAR CRYSTALS AND LIQUID CRYSTALS 356: 449-458 2001

A rational design of molecular materials, Fowler FW, Lauher JW JOURNAL OF PHYSICAL ORGANIC CHEMISTRY 13 (12): 850-857 DEC 2000

A supramolecular solution to a long-standing problem: The 1,6-polymerization of a triacetylene Xiao J, Yang M, Lauher JW, Fowler FW ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 39 (12): 2132-+ 2000

Thermochemistry: Fundamentals and application to the study of abused substances, Fowler FW, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 219: 7-TOXI Part 1 MAR 26 2000

Silver coordination and hydrogen bonds: A study of competing forces, Schauer CL, Matwey E, Fowler FW, Lauher JW MATERIALS RESEARCH BULLETIN : 213-223 Suppl. S NOV-DEC 1998

Design of molecular solids: utility of the hydroxyl functionality as a predictable design element Nguyen TL, Scott A, Dinkelmeyer B, Fowler FW, Lauher JW NEW JOURNAL OF CHEMISTRY 22 (2): 129-135 FEB 1998

N-phenyl-1-aza-2-cyano-1,3-butadienes: An intramolecular hetero Diels-Alder strategy for the construction of 1,4-benzodiazepines, Goulaouic-Dubois C, Adams DR, Sisti NJ, Fowler FW, Grierson DS, TETRAHEDRON LETTERS 39 (24): 4283-4286 JUN 11 1998

Controlled spacing of metal atoms via ligand hydrogen bonds Schauer CL, Matwey E, Fowler FW, Lauher JW JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 119 (42): 10245-10246 OCT 22 1997

Molecular symmetry and the design of molecular solids: The oxalamide functionality as a persistent hydrogen bonding unit Coe S, Kane JJ, Nguyen TL, Toledo LM, Wininger E, Fowler FW, Lauher JW JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 119 (1): 86-93 JAN 8 1997

The application of the 2-amino-4-pyrimidones to supramolecular synthesis Liao RF, Lauher JW, Fowler FW TETRAHEDRON 52 (9): 3153-3162 FEB 26 1996

Intramolecular Diels-Alder reaction of 2-cyano-1-aza-1,3-butadienes, Sisti NJ, Zeller E, Grierson DS, Fowler FW, JOURNAL OF ORGANIC CHEMISTRY 62 (7): 2093-2097 APR 4 1997

Intramolecular Diels-Alder reaction of N-alkyl-2-cyano-1-azadienes: A study of the Eschenmoser cycloreversion of dihydrooxazines as a route to N-alkyl-2-cyano-1-azadienes Motorina IA, Fowler FW, Grierson DS, JOURNAL OF ORGANIC CHEMISTRY 62 (7): 2098-2105 APR 4 1997

Reactivity of N-phenyl-1-aza-2-cyano-1,3,-butadienes in the Diels-Alder reaction, Sisti NJ, Motorina IA, Dau METH, Riche C, Fowler FW, Grierson DS, JOURNAL OF ORGANIC CHEMISTRY 61 (11): 3715-3728 MAY 31 1996

FLASH VACUUM THERMOLYSIS OF THE NONVOLATILE SUBSTRATES D-GLUCOSE AND D-MANNOSE, ZAIKOWSKI LA, FOWLER FW, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 210: 326-ORGN Part 2 AUG 20 1995

Preparation of layered diacetylenes as a demonstration of strategies for supramolecular synthesis Kane JJ, Liao RF, Lauher JW, Fowler FW JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 117 (48): 12003-12004 DEC 6 1995

Development of strategies for the preparation of designed solids - an investigation of the 2-amino-4(1h)-pyrimidone ring-system for the molecular self-assembly of hydrogen-bonded alpha-networks and beta-networks Toledo LM, Musa KM, Lauher JW, Fowler FW CHEMISTRY OF MATERIALS 7 (9): 1639-1647 SEP 1995

HIV REVERSE-TRANSCRIPTASE INHIBITORS - A CONCISE ENE REACTION-BASED SYNTHESIS OF THE 7,8-DIHYDRO-6H,12H-AZEPINO [2,1-B]QUINAZOLINE SYSTEM, AND ITS REACTION WITH NITRILE OXIDES, GOULAOUICDUBOIS C, ADAMS DR, CHIARONI A, RICHE C, FOWLER FW, GRIERSON DS, HETEROCYCLES 39 (2): 509-512 DEC 31 1994