Alternating Radical Stabilities: A Convergent Route to Terminal and Internal Boronates. (17th July 2019)

• Record Type: Journal Article
• Authors: Huang, Qi; Michalland, Jean; Zard, Samir Z.
• Is Part Of: Angewandte Chemie. Volume 131:Number 47(2019)
• Page Start: 17092
• Page End: 17098
• Publication Date: 2019-07-17
• Subjects: Aminoboronsäuren -- Boronate -- Radikaladditionen -- Radikalstabilitäten -- Xanthate; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201906497
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Pinacolato boronates (Bpin) with an empty p‐orbital on boron stabilize an adjacent carbon radical, in contrast to diethanolamino boronates [B(DEA)] where the boron is sp 3 ‐hybridized. By alternately placing a pinacol or diethanolamine moiety on the boron atom, thus stabilizing or not stabilizing the corresponding adjacent radical, it is possible to control the behavior of α‐boronyl xanthates and construct a large variety of terminal or internal boronates in a modular fashion. The remarkable tolerance of polar groups and the ability to introduce quaternary centers are particularly noteworthy features of this process. Abstract : Aufeinanderfolgende intermolekulare Radikaladditionen zur Synthese komplexer, hoch funktionalisierter Boronate können kontrolliert werden, indem die relativen Stabilitäten intermediärer Radikale durch die Änderung der Hybridisierung am Boratom von sp 2 zu sp 3 und umgekehrt angepasst werden.