2745-27-9Relevant articles and documents
Intramolecular carbenoid insertions: Reactions of α-diazo ketones derived from furanyl-, thienyl-, (benzofuranyl)-, and (benzothienyl)acetic acids with rhodium(II) acetate
Yong, Kelvin,Salim, Mohamed,Capretta, Alfredo
, p. 9828 - 9833 (1998)
α-Diazo ketones tethered to furan, benzofuran, thiophene, and benzothiophene by a single methylene spacer have been shown to undergo atypical, rhodium(II) acetate catalyzed chemistry. For example, while treatment of 1-diazo-3-(3-furanyl)-2-propanone with Rh2(OAc)4 resulted in the expected 2-(4-oxo-2-cyclopentenylidene)acetaldehyde, isomeric 1-diazo-3- (2-furanyl)-2-propanone undergoes a vinylogous Wolff rearrangement and in the presence of water gives a mixture of 6a-methyl-2,3,3a,6a-tetrahydrofuro [2,3- b]furan-2-one and 2-(2-methyl-3-furyl)acetic acid. Rhodium acetate catalyzed decomposition of 1-diazo-3-(3-benzofuranyl)-2-propanone and 1-diazo-3-(2- benzofuranyl)-2-propanone are also shown to undergo vinylogous Wolff rearrangement despite the fact that this chemistry is not observed with homologous benzofuranyl systems. α-Diazo ketones derived from benzothienyl propionic acids undergo the expected cyclization with 1-diazo-4-(3- benzothienyl)-2-butanone and 1-diazo-4-(2-benzothienyl)-2-butanone giving rise to 1,2,3,4-tetrahydrodibenzo[b,d]thiophen-3-one and 1,2,3,4- tetrahydrodibenzo[b,d]thiophen-2-one, respectively. While decomposition of 1- diazo-3(3-benzothienyl)-2-propanone resulted in the formation of 2,3-dihydro- 1H-benzo[b]cyclopenta[d]thiophen-2-one, the isomeric 1-diazo-3-(2- benzothienyl)-2-propanone gave a dimer which resulted from a [3 + 2] cycloaddition followed by a [1,3]-alkyl shift. Overall, the results from this study of intramolecular carbenoid insertion into five-membered heteroaromatic systems show that the resultant chemistry is dependent on the nature of the heteroatom, position of substitution, and the length of the aliphatic tether.
COMPOSITIONS AND METHODS OF TARGETING MUTANT K-RAS
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Paragraph 0112, (2018/04/20)
Compounds and compositions are presented that inhibit K-ras, and especially mutant K-ras. Certain compounds preferentially or even selectively inhibit specific forms of mutant K-Ras, and particularly the G12D mutant form.
Facile preparation of protected benzylic and heteroarylmethyl amines via room temperature Curtius rearrangement
Leathen, Matthew L.,Peterson, Emily A.
supporting information; experimental part, p. 2888 - 2891 (2010/06/14)
A step-wise, room temperature procedure for acyl azide formation and the subsequent Curtius rearrangement of phenyl and heteroaryl acetic acids is described. We have developed a protocol for room temperature Curtius rearrangement in MeOH or CHCl3 that provides an improvement over standard conditions, avoiding the use of additives or heat. This room temperature optimization of the Curtius rearrangement prevents the formation of side products often observed with benzylic acids, allowing access to a variety of benzylic and heteroarylmethyl amines.
