Unknown

Dataset Information

0

Diverse ring-opening reactions of rhodium η4-azaborete complexes.

ABSTRACT: Sequential treatment of [Rh(COE)2Cl]2 (COE = cyclooctene) with PiPr3, alkyne derivatives and t BuN[triple bond, length as m-dash]BMes (Mes = 2,4,6-trimethylphenyl) provided functionalized rhodium η4-1,2-azaborete complexes of the form (η4-azaborete)RhCl(PiPr3). The scope of this reaction was expanded to encompass alkynes with hydrogen, alkyl, aryl, ferrocenyl, alkynyl, azaborinyl and boronate ester substituents. Treatment of these complexes with PMe3 led to insertion of the rhodium atom into the B-C bond of the BNC2 ring, forming 1-rhoda-3,2-azaboroles. Addition of N-heterocyclic carbenes to azaborete complexes led to highly unusual rearrangements to rhodium η2,κ1-allenylborylamino complexes via deprotonation and C-N bond cleavage. Heating and photolysis of an azaborete complex also led to rupture of the C-N bond followed by subsequent rearrangements, yielding an η4-aminoborylallene complex and two isomeric η4-butadiene complexes.

SUBMITTER: Heß M 

PROVIDER: S-EPMC8163374 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Diverse ring-opening reactions of rhodium η<sup>4</sup>-azaborete complexes.

Heß Merlin M   Stennett Tom E TE   Fantuzzi Felipe F   Bertermann Rüdiger R   Schock Marvin M   Schäfer Marius M   Thiess Torsten T   Braunschweig Holger H  

Chemical science 20200804 34

Sequential treatment of [Rh(COE)<sub>2</sub>Cl]<sub>2</sub> (COE = cyclooctene) with P<sup>i</sup>Pr<sub>3</sub>, alkyne derivatives and <sup><i>t</i></sup> BuN[triple bond, length as m-dash]BMes (Mes = 2,4,6-trimethylphenyl) provided functionalized rhodium η<sup>4</sup>-1,2-azaborete complexes of the form (η<sup>4</sup>-azaborete)RhCl(P<sup>i</sup>Pr<sub>3</sub>). The scope of this reaction was expanded to encompass alkynes with hydrogen, alkyl, aryl, ferrocenyl, alkynyl, azaborinyl and boronat  ...[more]

Similar Datasets

Unknown Alkylative Aziridine Ring-Opening Reactions
| S-EPMC8003214 | biostudies-literature
Unknown Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation.
| S-EPMC5225450 | biostudies-literature
Unknown Ring-Opening Reactions of Phosphoramidate Heterocycles.
| S-EPMC10602049 | biostudies-literature
Unknown G-type Halohydrin Dehalogenases Catalyze Ring Opening Reactions of Cyclic Epoxides with Diverse Anionic Nucleophiles.
| S-EPMC10099379 | biostudies-literature
Unknown Rhodium-catalyzed asymmetric ring opening reactions of oxabicyclic alkenes: catalyst and substrate studies leading to a mechanistic working model.
| S-EPMC397404 | biostudies-literature
Unknown Ring-opening and ring-expansion reactions of carborane-fused borirane.
| S-EPMC8513813 | biostudies-literature
Unknown Highly Z- and enantioselective ring-opening/cross-metathesis reactions catalyzed by stereogenic-at-Mo adamantylimido complexes.
| S-EPMC2681245 | biostudies-literature
Unknown Rhodium(I)-catalyzed nucleophilic ring-opening reactions of oxabicyclo adducts derived from the [4 + 2]-cycloaddition of 2-imido-substituted furans.
| S-EPMC2495029 | biostudies-literature
Unknown Ring Opening Reactions of β-Propiolactam in Superacidic Media.
| S-EPMC9302645 | biostudies-literature
Unknown Flavin-enabled reductive and oxidative epoxide ring opening reactions.
| S-EPMC9391479 | biostudies-literature