Addition of Dimethylaminobismuth to Aldehydes, Ketones, Alkenes, and Alkynes

Abstract

Bi‐O‐Chemie: Bei einer direkten regioselektiven Route zu Bismut‐Bis(amino)naphthalin‐Verbindungen mit Bi‐O‐ und Bi‐C‐Bindungen wird eine Amidvorstufe mit Aldehyden, Ketonen, Alkenen und Alkinen umgesetzt, die unter Einschiebung in die Bi‐NMe2‐Bindung reagieren.

The Bis(allyl)bismuth Cation: A Reagent for Direct Allyl Transfer by Lewis Acid Activation and Controlled Radical Polymerization

“…22 In these reactions, addition of a second component, such as an allyltin compound, an allyl silane (Sakurai reaction), or the combination of an allyl halide and Fe 0 , Zn 0 or Sn 0 , was required 23. The direct carbometalation of a carbonyl substrate by a well‐defined organobismuth(III) compound alone (such as [BiMe 3 ] or [BiPh 3 ]) has not been observed to date 24–26. In agreement with these earlier reports, tris(allyl)bismuth ( 1 ) did not react with benzaldehyde in THF at ambient temperature.…”

“…From a mechanistic viewpoint, two different roles have been discussed for the bismuth center in allylations of aldehydes with bismuth catalysts: 1) Lewis acid activation of the substrate;6c and 2) transfer of the allyl ligand to the substrate (with possible simultaneous Lewis acid activation of the substrate) 21i. Our results provide the first evidence for the direct carbometalation of a carbonyl compound by a well‐defined organobismuth reagent 26. Furthermore, they show that Lewis acid activation of the substrate induced by cationization of the organobismuth reagent is essential.…”

A New Entry into Aluminum Chemistry: [L1AlMe]⋅THF, a Versatile Building Block for Bimetallic and Polymetallic Complexes

“…BiNMe 2 ] [10] reacts with 1 through the breaking of the Bi À NMe 2 bond and formation of a Bi À CH 2 bond. Bimetallic complex 4 is produced in good yield as a red solid, and is soluble in toluene, THF, benzene, and diethyl ether.…”

“…Melting points were measured in sealed glass tubes by using a Büchi B-540 melting point apparatus. Elemental analyses were performed by the Analytisches Labor des Instituts [8] [LSnCl], [8] [LAlCl(Me)], [6] [1,8-C 10 H 6 A C H T U N G T R E N N U N G (NSiMe 3 ) 2 BiNMe 2 ], [10] and Ca[N-A C H T U N G T R E N N U N G (SiMe 3 ) 2 ] 2 ·2 THF [7] were prepared according to literature procedures.…”

Das Bis(allyl)bismut‐Kation: ein Reagens für direkte Allyl‐ Übertragung und kontrollierte radikalische Polymerisation

“…22 Dabei wird eine zweite Komponente wie eine Allylzinnverbindung, ein Allylsilan (Sakurai‐Reaktion) oder die Kombination eines Allylhalogenids mit Fe 0 , Zn 0 oder Sn 0 benötigt 23. Die direkte Carbometallierung eines Carbonylsubstrats allein durch eine wohldefinierte Organobismut(III)‐Verbindung (wie [BiMe 3 ] oder [BiPh 3 ]) wurde noch nicht beobachtet 24–26. In Übereinstimmung mit diesen früheren Arbeiten reagierte Tris(allyl)bismut ( 1 ) bei 23 °C in THF nicht mit Benzaldehyd.…”