2769-71-3Relevant articles and documents
Heterocyclopentanediyls vs heterocyclopentadienes: A question of silyl group migration
Beer, Henrik,Bresien, Jonas,Michalik, Dirk,R?lke, Anne-Kristin,Schulz, Axel,Villinger, Alexander,Wustrack, Ronald
supporting information, p. 14435 - 14445 (2020/12/29)
The reaction of the singlet biradical [P(μ-NHyp)]2 (Hyp = hypersilyl, (Me3Si)3Si) with different isonitriles afforded a series of five-membered N2P2C heterocycles. Depending on the steric bulk of the substituent at the isonitrile, migration of a Hyp group was observed, resulting in two structurally similar but electronically very different isomers. As evidenced by comprehensive spectroscopic and theoretical studies, the heterocyclopentadiene isomer may be regarded as a rather unreactive closed-shell singlet species with one localized N=P and one C=P double bond, whereas the heterocyclopentanediyl isomer represents an open-shell singlet biradical with interesting photochemical properties, such as photoisomerization under irradiation with red light to a [2.1.0]- housane-type species.
Reversible switching between housane and cyclopentanediyl isomers: An isonitrile-catalysed thermal reverse reaction
Beer, Henrik,Bresien, Jonas,Michalik, Dirk,Schulz, Axel,Villinger, Alexander
supporting information, p. 13986 - 13992 (2020/11/02)
The photo-isomerization of an isolable five-membered singlet biradical based on C, N, and P ([TerNP]2CNDmp, 2a) selectively afforded a closed-shell housane-type isomer (3a) by forming a transannular P-P bond. In the dark, the housane-type species re-isomerized to the biradical, resulting in a fully reversible overall process. In the present study, the influence of tBuNC on the thermal reverse reaction was investigated: The isonitrile acted as a catalyst, thus allowing control over the thermal reaction rate. Moreover, tBuNC also reacted with the biradical to form an adductspecies ([TerNP]2CNDmp·CNtBu, 4a), which can be regarded as the resting state of the system. The reactive species 2a and 3a could be re-generated in situ by irradiation with red light. The results of this study extend our understanding of this new class of molecular switches.
Magnesium Aldimines Prepared by Addition of Organomagnesium Halides to 2,4,6-Trichlorophenyl Isocyanide: Synthesis of 1,2-Dicarbonyl Derivatives
Schw?rzer, Kuno,Bellan, Andreas,Z?schg, Maximilian,Karaghiosoff, Konstantin,Knochel, Paul
, p. 9415 - 9418 (2019/05/10)
The selective addition of organomagnesium reagents to 2,4,6-trichlorophenyl isocyanide leading to magnesiated aldimines is reported. These aldimines react with Weinreb amides, ketones, or carbonates to provide the corresponding carbonyl derivatives after acidic cleavage. This allows for an efficient synthesis of 1,2-dicarbonyl compounds and α-hydroxy ketones.