Synthetic Organic and Physical Organic Chemistry
Teaching: Graduate & undergraduate organic chem
Area of Research
SNAAP® Alkylation Chemistry of Sulfonimidates
Dr. Maricich's research involves syntheses, reactions, mechanisms, and stereochemistry of SNAAP® alkylations of various nucleophiles by sulfonimidate esters. SNAAP® (Substitution, Nucleophilic of Acids, Alcohols and Phenols) refers to alkylation of alcohols by N-tert-butyl-O-ethyl-4-nitrobenzenesulfonimidate, which produced unrearranged ethyl ethers in high yields at room temperature within twenty minutes, when catalyzed by the tetrafluoroboric acid dimethyl ether complex. No rearrangements were observed in the ether products formed from 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, neopentyl alcohol, 3-buten-2-ol, menthol, 1-phenylethanol or cinnamyl alcohol. Optically active menthol was ethylated with complete retention of configuration.
This work was published in December 2013 as a full paper in Synthesis 2013; 45(24): 3361-3368. DOI: 10.1055/s-0033-1339921, entitled SNAAP Sulfonimidate Alkylating Agents for Acids, Alcohols and Phenols on the work of five M.S. and thirteen undergraduate students at CSULB. The key reagent [ethyl N-tert-butyl-4-nitrobenzenesulfonimidate] reported in their paper is now available as the "Maricich ethylation reagent" from Aldrich Chemical Company (Catalog # L512311).
Abstract: Stable, crystalline N-tert-butyl-O-ethyl-4-nitrobenzene-sulfonimidate has been prepared in high yield by direct O-ethylation of N-tert-butyl-4-nitro-benzenesulfonamide with iodoethane and silver in methylene chloride. This sulfonimidate directly ethylates various acids to esters. The stronger the acid, the faster it alkylates and in higher yield. It readily ethylates alcohols and phenols to ethers at room temperature in the presence of HBF4 catalyst without molecular rearrangements or racemization. We have defined these reactions as SNAAP® alkylations:. The hard sulfonimidate alkylating agent is chemoselective, preferrring oxygen > nitrogen > sulfur. The sulfonamide byproduct of alkylation is readily recycled to the sulfonimidate.
Future studies will include alkylations of biomolecules like estrogen and cyclic-AMP, competition between various nucleophiles, and reactions of chiral sulfonimidates with prochiral phosphoric and phosphonic acids and with hemiacetals.
Dr. Maricich is continuing in his lab as a full-time emeritus faculty doing writing and research with undergraduates and research volunteers. They are studying new sulfonimidate alkylation reactions, especially those with isopropyl as the alkylating group. In addition to the predominant O-alkylation of phenols, some electrophilic aromatic substitution has been observed.
University of Washington, Seattle, Washington, B.S., 1961, Chemistry
Yale University, New Haven, Connecticut, M.S., 1963, Ph.D., 1965, Chemistry
- The Chemistry of Alkyl Sulfonimidates, California State University, Long Beach, December, 2004.
- Andrea I. Chen (presenter), Tom J. Maricich, Dustin Wride, Matthew J. Allan, Brett Kislin, and Nguyen-Phuong Pham, .Alkylation Reactions of O-Alkyl Sulfonimidates,. 40th Western Regional Meeting of The American Chemical Society (Anaheim), Paper No. 127, January 2006.
- Outstanding Undergraduate Poster Award at the American Chemical Society Western Regional Meeting 2007 Frontiers in Chemistry, Biopharmaceuticals & Biotechnology in San Diego October 9-13, 2007. We were acknowledged at the meeting and awarded one of five awards [out of sixty posters] for our poster entitled "Facile, One-Step Alkylation of Alcohols and Phenols by N-t-Butyl-O-Ethyl-p-Nitrobenzenesulfonimidate," by Christine Bradford, Nai-Chia Kuan, Jeremy Wood and Tom J. Maricich, California State University, Long Beach, Long Beach, CA [Abstract #443].
Research Assistants at CSULB
- Andrea Chen (M.S.)
- Daniel Savino (President's Scholar)
- Christine Bradford (President's Scholar)
- Gretchen Witowich (President's Scholar)
- Alethea Poste (HHMI Scholar)
- Omonigho Aisagbonhi (HHMI Scholar)
- Melissa Garza (RISE Fellow)
- Dustin Wride
- Douglas Thai
- Sylvia Kim (summer research assistant from Wellesley College)
- Andrew Roberts (summer research assistant from UC San Diego)
- Naoki Kodama
- Fan-Chun (Renata) Meng (M.S.)
- Igor Izotov (M.S. candidate)
- Michael Fimbres (M.S. candidate)
- Nai-Chia Kuan (Provost Scholar)
- Jeremy Wood (Provost Scholar)
- Francisco Rodriguez (Robert B. Henderson Memorial Scholar, Robert D. Rhodes Award)
- Marilyn Ton
- Holly Phung
- Sokrith Sea
Consultant to: Cal OSHA, 1998; Lava Louie, Long Beach, CA, 2005; Intelligent Energy, Ltd., Long Beach, CA, 2007.
Expert chemical witness and consultant to various law firms in litigations related to chemical safety, personal injury, environmental pollution, fire, and explosions for both plaintiffs and defendants, 1986-present.
Among other activities, Dr. Maricich has devoted time to teaching chemistry to primary school students!