skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Deoxygenation of Unhindered Alcohols via Reductive Dealkylation of Derived Phosphate Esters

Abstract

Primary alcohols can be deoxygenated cleanly and in high yield by reduction of derived diphenyl phosphate esters with lithium triethylborohydride in tetrahydrofuran at room temperature. Selective deoxygenation of a primary alcohol in the presence of a secondary alcohol was demonstrated. The two-step process can be performed in one pot, making it both simple and convenient.

Authors:
 [1];  [2]
  1. Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Biochemistry and Cellular & Molecular Biology
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; Work for Others (WFO)
OSTI Identifier:
1327565
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Organic Chemistry
Additional Journal Information:
Journal Volume: 81; Journal ID: ISSN 0022-3263
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; deoxygenation; phosphorus chemistry; green chemistry; reduction; organic synthesis

Citation Formats

Chowdhury, Sarwat, and Standaert, Robert F. Deoxygenation of Unhindered Alcohols via Reductive Dealkylation of Derived Phosphate Esters. United States: N. p., 2016. Web. doi:10.1021/acs.joc.6b01699.
Chowdhury, Sarwat, & Standaert, Robert F. Deoxygenation of Unhindered Alcohols via Reductive Dealkylation of Derived Phosphate Esters. United States. doi:10.1021/acs.joc.6b01699.
Chowdhury, Sarwat, and Standaert, Robert F. 2016. "Deoxygenation of Unhindered Alcohols via Reductive Dealkylation of Derived Phosphate Esters". United States. doi:10.1021/acs.joc.6b01699. https://www.osti.gov/servlets/purl/1327565.
@article{osti_1327565,
title = {Deoxygenation of Unhindered Alcohols via Reductive Dealkylation of Derived Phosphate Esters},
author = {Chowdhury, Sarwat and Standaert, Robert F.},
abstractNote = {Primary alcohols can be deoxygenated cleanly and in high yield by reduction of derived diphenyl phosphate esters with lithium triethylborohydride in tetrahydrofuran at room temperature. Selective deoxygenation of a primary alcohol in the presence of a secondary alcohol was demonstrated. The two-step process can be performed in one pot, making it both simple and convenient.},
doi = {10.1021/acs.joc.6b01699},
journal = {Journal of Organic Chemistry},
number = ,
volume = 81,
place = {United States},
year = 2016,
month = 9
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:
  • Lithium trialkylborohydrides were found to effect rapid monodealkylation of phosphonic diesters, and this reaction was applied to the synthesis of alkylphosphonic acid 2-aminoethyl esters [H2N(CH2)2OP(OH)R, 4], a little-explored class of analogs of the inhibitory neurotransmitter γ-aminobutyric acid (GABA). Compound 4a (R = Me) proved to be a potent antagonist at human ρ1 GABAC receptors (expressed in Xenopus laevis oocytes), with an IC50 of 11.1 M, but is inactive at α1β2γ2 GABAA receptors.
  • The catalytic activity of ..cap alpha..-Zr(HPO/sub 4/)/sub 2/ x H/sub 2/O prepared by different methods and of phases derived from it by heating between 200 and 1100/sup 0/C or by ion exchange with Na/sup +/, Cs/sup +/, or Ag/sup +/, has been investigated by means of different acid-catalyzed test reactions, namely, isopropanol, 1- or 2-butanol dehydration, and 1-butene isomerization. The active centers of both Zr(HPO/sub 4/)/sub 2/ and ZrP/sub 2/O/sub 7/ phases are mainly the surface Broensted sites, as indicated by the strong decrease or annihilation of their catalytic activity after surface Cs/sup +/ poisoning. An explanation of the lowmore » residual activity detected for same samples is given. As deduced from the products of 1-butene isomerization, the acidic sites are generally of medium strength. However, on heating between 350 and 700/sup 0/C, when partial or total condensation of hydrogen phosphate to P-O-P groups occurs (with progressive formation of the layered pyrophosphate phase) they transform into sites of medium-high strength.« less
  • An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(Ox Me²)(Ox Me²SiHPh)Im Mes}Rh(H)CO][HB(C₆F₅)₃] (2, Ox Me² = 4,4-dimethyl-2-oxazoline; Im Mes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(Ox Me²)₂Im Mes}RhH(SiH 2Ph)CO (1) and B(C 6F 5) 3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(Ox Me²)₂Im Mes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced bymore » the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenation of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less