| Reference | [1]. Org Lett. 2019 Jul 19;21(14):5611-5615. doi: 10.1021/acs.orglett.9b01959. Epub 2019 Jun 28.<br />
Triphosgene and DMAP as Mild Reagents for Chemoselective Dehydration of Tertiary Alcohols.<br />
Ganiu MO(1), Cleveland AH(1), Paul JL(1), Kartika R(1).<br />
Author information: (1)Department of Chemistry , Louisiana State University , 232 Choppin Hall , Baton Rouge , Louisiana 70803 , United States.<br />
The utility of triphosgene and DMAP as mild reagents for chemoselective dehydration of tertiary alcohols is reported. Performed in dichloromethane at room temperature, this reaction is readily tolerated by a broad scope of substrates, yielding alkenes preferentially with the (E)-geometry. While formation of the Hofmann products is generally favored, a dramatic change in alkene selectivity toward the Zaitzev products is observed when the reaction is carried out in dichloroethane at reflux.<br />
DOI: 10.1021/acs.orglett.9b01959 PMID: 31251637<br />
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[2]. Anal Chem. 2019 May 7;91(9):5690-5697. doi: 10.1021/acs.analchem.8b05777. Epub 2019 Apr 25.<br />
Fluorescent Chemosensor for Dual-Channel Discrimination between Phosgene and Triphosgene.<br />
Wang SL(1), Li C(1), Song QH(1).<br />
Author information: (1)Department of Chemistry , University of Science and Technology of China , Hefei 230026 , P. R. China.<br />
As highly toxic and accessible chemical reagents, phosgene and triphosgene have become a serious threat to public safety. So, it is highly desirable to develop facile methods to detect and recognize them. In this article, a novel fluorescent chemosensor, Phos-4, has been constructed with 1,8-naphthalimide as the fluorophore and 2-(2-aminophenyl)imidazol as the recognition sites for discrimination between phosgene and triphosgene in a dual-channel mode for the first time. Owing to the difference in electrophilicity between chlorocarbonyl and trichloromethoxycarbonyl, the sensing reaction of Phos-4 with phosgene undergoes two carbamylations to afford a cyclic product with green fluorescence, and only one carbamylation occurs for triphosgene to form a noncyclic product with blue fluorescence. The sensor Phos-4 exhibits high sensitivity (the limit of detection, 3.2 nM, for phosgene, and 1.9 nM, for triphosgene) and high selectivity in solutions. Furthermore, facile test papers containing Phos-4-embedded nanofibrous membrane have been fabricated by the electrospinning technology. The test papers can provide visual and selective detection of phosgene with a lower limit of detection (42 ppb) and a faster response (≤10 s) in the gas phase over those in solutions. The test paper with Phos-4 is promising to be a practical detection tool of gaseous phosgene.<br />
DOI: 10.1021/acs.analchem.8b05777 PMID: 30994328 [Indexed for MEDLINE]<br />
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[3]. Tetrahedron. 2020 Nov 20;76(47):131553. doi: 10.1016/j.tet.2020.131553. Epub 2020 Sep 6.<br />
A decade review of triphosgene and its applications in organic reactions.<br />
Ganiu MO(1), Nepal B(1), Van Houten JP(1), Kartika R(1).<br />
Author information: (1)Department of Chemistry, 232 Choppin Hall, Louisiana State University, Baton Rouge, LA 70803 United States.<br />
This review article highlights selected advances in triphosgene-enabled organic synthetic reactions that were reported in the decade of 2010-2019. Triphosgene is a versatile reagent in organic synthesis. It serves as a convenient substitute for the toxic phosgene gas. Despite its first known preparation in the late 19th interestingly began only three decades ago. Despite the relatively short history, triphosgene has been proven to be very useful in facilitating the preparation of a vast scope of value-added compounds, such as organohalides, acid chlorides, isocyanates, carbonyl addition adducts, heterocycles, among others. Furthermore, applications of triphosgene in complex molecules synthesis, polymer synthesis, and other techniques, such as flow chemistry and solid phase synthesis, have also emerged in the literature.<br />
DOI: 10.1016/j.tet.2020.131553 PMCID: PMC8054975 PMID: 33883783<br />
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[4]. Chem Commun (Camb). 2015 Oct 18;51(81):15075-8. doi: 10.1039/c5cc06365e.<br />
Triphosgene-pyridine mediated stereoselective chlorination of acyclic aliphatic 1,3-diols.<br />
Villalpando A(1), Saputra MA, Tugwell TH, Kartika R.<br />
Author information: (1)Department of Chemistry, 232 Choppin Hall, Louisiana State University, Baton Rouge, LA 70803, USA. [email protected].<br />
We describe a strategy to chlorinate stereocomplementary acyclic aliphatic 1,3-diols using a mixture of triphosgene and pyridine. While 1,3-anti diols readily led to 1,3-anti dichlorides, 1,3-syn diols must be converted to 1,3-syn diol monosilylethers to access the corresponding 1,3-syn dichlorides. These dichlorination protocols were operationally simple, very mild, and readily tolerated by advanced synthetic intermediates.<br />
DOI: 10.1039/c5cc06365e PMCID: PMC4599979 PMID: 26323232 [Indexed for MEDLINE]<br />
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[5]. J Org Chem. 2013 Apr 19;78(8):3989-96. doi: 10.1021/jo400341n. Epub 2013 Mar 29.<br />
Triphosgene-amine base promoted chlorination of unactivated aliphatic alcohols.<br />
Villalpando A(1), Ayala CE, Watson CB, Kartika R.<br />
Author information: (1)Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, Louisiana 70803, USA.<br />
Unactivated α-branched primary and secondary aliphatic alcohols have been successfully transformed into their corresponding alkyl chlorides in high yields upon treatment with a mixture of triphosgene and pyridine in dichloromethane at reflux. These mild chlorination conditions are high yielding, stereospecific, and well tolerated by numerous sensitive functionalities. Furthermore, no nuisance waste products are generated in the course of the reactions.<br />
DOI: 10.1021/jo400341n PMCID: PMC4153350 PMID: 23496045
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