Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon-boron bond into a carbon-X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row d-block transition metals have become increasingly widely used as catalysts for the formation of a carbon-boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon-boron bonds.

First-Row d-Block Element-Catalyzed Carbon-Boron Bond Formation and Related Processes.

This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12-16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

Molecular Main Group Metal Hydrides

Organolithium compounds have been at the forefront of synthetic chemistry for over a century, as they mediate the synthesis of myriads of compounds that are utilised worldwide in academic and industrial settings. For that reason, lithium has always been the most important alkali metal in organometallic chemistry. Today, that importance is being seriously challenged by sodium and potassium, as the alkali-metal mediation of organic reactions in general has started branching off in several new directions. Recent examples covering main-group homogeneous catalysis, stoichiometric organic synthesis, low-valent main-group metal chemistry, polymerization, and green chemistry are showcased in this Review. Since alkali-metal compounds are often not the end products of these applications, their roles are rarely given top billing. Thus, this Review has been written to alert the community to this rising unifying phenomenon of "alkali-metal mediation".

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202010963

Alkali-metal mediation: diversity of applications in main-group organometallic chemistry

The use of transition metals to catalyse the addition of hydridoboranes to unsaturated organic molecules was initially realised several decades ago. Although this area of chemistry received considerable attention at the time, interest in this reaction and its use in organic synthesis waned for several years. Like a phoenix rising from the ashes, this amazing catalytic reaction has grown to include the use of earth-abundant metal catalysts and a much wider range of organic substrates. Indeed, it is now commonly utilised as a diagnostic tool to assess the reactivity and catalytic ability of newly generated transition metal and main group complexes. As this field is progressing so rapidly, this review highlights some important advances up to the end of 2021 and into early 2022. Excluded from this review are 'hydroboration' reactions using diboron sources.

/pdf/the-transition-metal-catalysed-hydroboration-reaction-18livkim.pdf

The transition metal-catalysed hydroboration reaction.

Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin.

The continued development of hydroboration catalysts typifies the importance of this transformation as a testbed for catalytic activity and as a fundamental reaction for organic synthesis. Catalyti...

The Hidden Role of Boranes and Borohydrides in Hydroboration Catalysis

This review highlights transborylation (controlled boron-boron exchange) and its applications as a turnover strategy in boron-catalysed methodologies. Catalytic applications of B–C, B–O, B–N, B–F, B–S, and B–Se transborylations are discussed in the context of transborylation-enabled catalysis, across a wide range of organic transformations including hydroboration, C–C bond formation, C–H borylation, chemoselective reduction, and asymmetric reduction.1 Introduction2 B–C Transborylation3 B–O Transborylation4 B–N Transborylation5 B–F Transborylation6 B–S Transborylation7 Conclusion

/pdf/transborylation-enabled-boron-catalysis-24gbnrrz.pdf

Transborylation-Enabled Boron Catalysis

The asymmetric reduction of ketones with pinacolborane (HBpin) has been catalysed by an enantioenriched borane catalyst, formed in situ from 9-borabicyclo[3.3.1]nonane (H-B-9-BBN) and β-pinene. While previously only used stoichiometrically, this borane has now been rendered catalytic using a new turnover mechanism, B-O transborylation. Thermodynamic and kinetic parameters of the key B-O/B-H transborylation showed this is a sub-class of σ-bond metathesis.

A Boron-Oxygen Transborylation Strategy for the Asymmetric Reduction of Ketones

The mechanism of R2BH-catalyzed hydroboration of alkynes by 1,3,2-dioxaborolanes has been investigated by in situ 19F NMR spectroscopy, kinetic simulation, isotope entrainment, single-turnover labeling (10B/2H), and density functional theory (DFT) calculations. For the Cy2BH-catalyzed hydroboration 4-fluorophenylacetylene by pinacolborane, the resting state is the anti-Markovnikov addition product ArCH = CHBCy2. Irreversible and turnover-rate limiting reaction with pinacolborane (k ≈ 7 × 10–3 M–1 s–1) regenerates Cy2BH and releases E-Ar–CH═CHBpin. Two irreversible events proceed in concert with turnover. The first is a Markovnikov hydroboration leading to regioisomeric Ar–C(Bpin)═CH2. This is unreactive to pinacolborane at ambient temperature, resulting in catalyst inhibition every ∼102 turnovers. The second is hydroboration of the alkenylboronate to give ArCH2CH(BCy2)Bpin, again leading to catalyst inhibition. 9-BBN behaves analogously to Cy2BH, but with higher anti-Markovnikov selectivity, a lower barri...

/pdf/kinetics-and-mechanism-of-the-arase-hoshi-r2bh-catalyzed-3ds3ntht0l.pdf

Kinetics and Mechanism of the Arase-Hoshi R2BH-Catalyzed Alkyne Hydroboration: Alkenylboronate Generation via B–H/C–B Metathesis

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