Diisobutylaluminum Hydride

Galatsis, Paul; Sollogoub, Matthieu; Sînaÿ, Pierre

doi:10.1002/047084289x.rd245.pub2

Cited by 7 publications

(5 citation statements)

References 59 publications

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“…Neutral aluminium hydride reagents (i.e. R 1 R 2 Al-H) are useful reagents in organic synthesis, [1] and species such as alane (AlH 3 ) have also attracted interest as hydrogen storage materials, demonstrating potential application as a rocket propellant [2] and as a hydrogen source for portable fuel cells. [3,4] Besides the potential technological applications of alane, we note that attention has also been given to ways in which nonpolymerised forms of this reagent may be prepared and used in synthetic chemistry.…”

Section: Introductionmentioning

confidence: 99%

Highly accurate CCSD(T) homolytic Al–H bond dissociation enthalpies – chemical insights and performance of density functional theory

O'Reilly

Karton

2023

Aust. J. Chem.

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We obtain gas-phase homolytic Al–H bond dissociation enthalpies (BDEs) at the CCSD(T)/CBS level for a set of neutral aluminium hydrides (which we refer to as the AlHBDE dataset). The Al–H BDEs in this dataset differ by as much as 79.2 kJ mol−1, with (H2B)2Al–H having the lowest BDE (288.1 kJ mol−1) and (H2N)2Al–H having the largest (367.3 kJ mol−1). These results show that substitution with at least one –AlH2 or –BH2 substituent exerts by far the greatest effect in modifying the Al–H BDEs compared with the BDE of monomeric H2Al–H (354.3 kJ mol−1). To facilitate quantum chemical investigations of large aluminium hydrides, for which the use of rigorous methods such as W2w may not be computationally feasible, we assess the performance of 53 density functional theory (DFT) functionals. We find that the performance of the DFT methods does not strictly improve along the rungs of Jacob’s Ladder. The best-performing methods from each rung of Jacob’s Ladder are (mean absolute deviations are given in parentheses): the GGA B97-D (6.9), the meta-GGA M06-L (2.3), the global hybrid-GGA SOGGA11-X (3.3), the range-separated hybrid-GGA CAM-B3LYP (2.1), the hybrid-meta-GGA ωB97M-V (2.5) and the double-hybrid methods mPW2-PLYP and B2GP-PLYP (4.1 kJ mol−1).

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Section: Introductionmentioning

confidence: 99%

Highly accurate CCSD(T) homolytic Al–H bond dissociation enthalpies – chemical insights and performance of density functional theory

O'Reilly

Karton

2023

Aust. J. Chem.

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“…Conventionally, partial reduction of esters is accomplished by using bulky metal hydrides, such as diisobutylaluminum hydride (DIBAL), through the generation of a stable tetrahedral intermediate ( Int-A ) that does not collapse to aldehyde during the reaction (Figure A) . In the context of catalytic hydrosilylation, we envision that the key to alternating the desymmetrization product lies in the control of reaction pathways of an analogous zinc hemiacetal Int-B from the hydride addition.…”

Section: Introductionmentioning

confidence: 99%

Desymmetric Partial Reduction of Malonic Esters

Liu

Huang

2022

J. Am. Chem. Soc.

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Desymmetrization of easily available disubstituted malonic esters is a rewarding strategy to access structurally diverse quaternary stereocenters. Particularly, asymmetric reduction of malonic esters would generate a functional group with a lower oxidation state than the remaining ester, thus allowing for more chemoselective derivatization. Here, we report a new set of conditions for the zinccatalyzed desymmetric hydrosilylation of malonic esters that afford aldehydes as the major product. Compared with alcohol-selective desymmetrization, the partial reduction uses a higher concentration of silanes and new pipecolinol-derived tetradentate ligands, proposedly to switch the pathway of zinc hemiacetal intermediates from elimination to silylation. As a result, high aldehyde-to-alcohol ratios and enantioselectivity of aldehydes are obtained from malonic esters with a large collection of substituents. Together with the abundant reactivity of aldehydes, the partial reduction has enabled an expeditious synthesis of bioactive compounds and natural metabolites containing a quaternary stereocenter.

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“…While many of these chemical approaches have been reported at large scale (>100 mmol) in the pharmaceutical industry, one area that shows a conspicuous lack of large-scale examples is the direct reduction of esters to aldehydes . A commonly invoked reagent for such a transformation on the lab scale is diisobutylaluminum hydride (DIBAL-H), yet this reagent is not nearly as commonly encountered on large scales, likely because of multiple process challenges, including the strongly exothermic nature of the reaction and the formation of high levels of impurities as a result of over-reduction, especially at noncryogenic temperatures …”

Section: Introductionmentioning

confidence: 99%

Selective DIBAL-H Monoreduction of a Diester Using Continuous Flow Chemistry: From Benchtop to Kilo Lab

Uhlig¹,

Martins²,

Gao³

2020

Org. Process Res. Dev.

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Herein we report a selective DIBAL-H-mediated reduction of a heterocyclic diester to the corresponding monoaldehyde using continuous flow chemistry. The use of continuous flow enabled operation at lower temperatures and better control of the reaction time, thereby allowing for a significant increase in reaction selectivity and yield compared with batch conditions. The reaction’s development as a continuous flow process and its scale-up from laboratory gram scale to multikilogram scale are discussed, including design of experiments studies to probe the optimal reaction window.

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Diisobutylaluminum Hydride

Cited by 7 publications

References 59 publications

Highly accurate CCSD(T) homolytic Al–H bond dissociation enthalpies – chemical insights and performance of density functional theory

Highly accurate CCSD(T) homolytic Al–H bond dissociation enthalpies – chemical insights and performance of density functional theory

Desymmetric Partial Reduction of Malonic Esters

Selective DIBAL-H Monoreduction of a Diester Using Continuous Flow Chemistry: From Benchtop to Kilo Lab

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