A decade review of triphosgene and its applications in organic reactions

Abstract

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.

Keywords: Bis(trichloromethyl) carbonate; Carbonyl compounds; Heterocycles; Organohalides; Triphosgene.

Fig. 1.

Triphosgene and journal publication trend.

Scheme 1.

Synthesis of Alkyl Chlorides.

Scheme 2.

Synthesis of Alkyl Chlorides via Addition - Ring Expansion Reactions.

Scheme 3.

Synthesis of Alkyl 1,2-Dichlorides.

Scheme 4.

Synthesis of Alkyl 1,3-Dichlorides and 1,3,5-Trichlorides.

Scheme 5.

Synthesis of Vinyl Chlorides.

Scheme 6.

Synthesis of Aryl Chlorides.

Scheme 7.

Synthesis of Chlorocarbonates.

Scheme 8.

Synthesis of Aryl Bromides.

Scheme 9.

Synthesis of Isocyanates and Isothiocyanates.

Scheme 10.

Synthesis of Trichloromethyl Carbamates.

Scheme 11.

Dehydration of Alcohols.

Scheme 12.

Oxidation of Alcohols.

Scheme 13.

Synthesis of Metal-Carbyne Complex.

Scheme 14.

Synthesis of Acid Chlorides.

Scheme 15.

Synthesis of Chloroformates.

Scheme 16.

Synthesis of Carbamoyl Chlorides.

Scheme 17.

Synthesis of Acid Anhydrides.

Scheme 18.

Synthesis of Amides.

Scheme 19.

Synthesis of Pyrrolizinones.

Scheme 20.

Synthesis of Carbonates and Thiocarbonates.

Scheme 21.

Synthesis of Carbamates.

Scheme 22.

Synthesis of Oxazolidinones from 1,2-aminoalcohols.

Scheme 23.

Synthesis of Oxazolidinones to Deduce Stereochemistry.

Scheme 24.

Synthesis of Benzoxazolones.

Scheme 25.

Synthesis of Benzoxazinones from Phenol-Derived Ketimines.

Scheme 26.

Synthesis of Benzoxazinone Dimers.

Scheme 27.

Synthesis of Oxadiazolones.

Scheme 28.

Synthesis of Isatoic Anhydrides.

Scheme 29.

Synthesis of Symmetrical Ureas.

Scheme 30.

Synthesis of Unsymmetrical Ureas.

Scheme 31.

Synthesis of Cyclic Ureas.

Scheme 32.

Synthesis of Macrocyclic Ureas.

Scheme 33.

Synthesis of Uracils.

Scheme 34.

Synthesis of Quinazolidinones.

Scheme 35.

Synthesis of Imidazolidinones.

Scheme 36.

Synthesis of Imidazopyridines.

Scheme 37.

Synthesis of Triazolidine-3,5-Diones.

Scheme 38.

Synthesis of Selenodiazolones.

Scheme 39.

Synthesis of Pyrimidinones.

Scheme 40.

Synthesis of Pyrazoles.

Scheme 41.

Synthesis of Oxazoles.

Scheme 42.

Synthesis of 2,4-Dichloroquinazolines.

Scheme 43.

Synthesis of Polycarbonates.

Scheme 44.

Flow Synthesis of Chloroformates.

Scheme 45.

Flow Synthesis of Amides.

Scheme 46.

Flow Synthesis of Peptides.

Scheme 47.

Flow Synthesis of Cyclic RGD Pentapeptides.

Scheme 48.

Flow Synthesis of Ureas.

Scheme 49.

Flow Synthesis of Triazoles.

Scheme 50.

Solid Phase Synthesis of Oligoamides.

Scheme 51.

Solid Phase Peptide Synthesis of Natural Products.

Scheme 52.

Solid Phase Peptide Synthesis Using Unreactive Amines.