Recent Advances in the Synthesis of Acylboranes and Their Widening Applicability

Abstract

The most common types of acylboranes are acyltrifluoroborates, acyl MIDA-boronates, and monofluoroacylboronates. Because of the increasing importance of these compounds in the past decade, we highlight the recently reported synthetic strategies to access acylboranes. In addition, an expanding array of their applications has been discovered, based on either the ability of acylboranes to enter rapid amide-forming ligations or the retained ketone-like character of the carbonyl group. Therefore, we also describe ground-breaking achievements where acylboranes were successfully put to use, such as their utility in biochemical, material, and medicinal sciences.

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

“…This allows for the preparation of various functionalized MIDA boronate building blocks, including, for example, unusual acyl derivatives 16-18 shown in Figure 4. [124][125][126][127] It should be outlined that some aspects of the aforementioned approaches (i. e. the CÀ B bond formation via radical intermediates, [128] as well as transition metal-free methods [129] ) were recently reviewed.…”

Boron-promoted Deprotonative Conjugate Addition: Development of Geminal diborons as Versatile Soft Pronucleophiles and Acyl An-ion Equivalents

“…The unique chemical reactivity and applications of acylborons in organic synthesis and bioconjugation have inspired several creative synthetic methods. 25,26 While the α-keto 27 and β-keto acylborons 28 can be prepared using several approaches, methods to access γ-keto acylborons are scarce. 29 Inspired by our recently developed route to MIDA acylborons, 15,16 the geminal diboron motif in the conjugate addition product 3y (Scheme 4) was successfully transformed into the unsymmetrical diboron 6.…”

Acyl metalloids: conformity and deviation from carbonyl reactivity

“…In comparison to other acyl metalloids, acylboron species remained elusive until the late 2000s. [3][4][5] Initially, these compounds were proposed as intermediates in several transformations, but their isolation and characterization were not realized due to their presumed susceptibility to oxidation and rearrangement. [6][7][8][9][10][11] The first example of an isolable acylboron compound was reported by Nozaki and coworkers in 2007, who accessed this class of compounds by reacting borylmagnesium 1 with benzaldehyde (Scheme 1a).…”