Wittig Rearrangements of Boron-Based Oxazolidinone Enolates

Zhang, Zirong; Collum, David B.

doi:10.1021/acs.joc.9b01426

Cited by 7 publications

(3 citation statements)

References 36 publications

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“…However, some reaction types that are important in organic chemistry, such as pericyclic, hydride-transfer, and halogen-atom transfer reactions, are relatively rare in biological contexts or are not sufficiently represented in the M-CSA. For these reaction types, we explored the literature and compiled a number of reactions from various published mechanistic studies to complete our database. − …”

Section: Design Of Bh9 and Computational Detailsmentioning

confidence: 99%

BH9, a New Comprehensive Benchmark Data Set for Barrier Heights and Reaction Energies: Assessment of Density Functional Approximations and Basis Set Incompleteness Potentials

Prasad

Pei

Edelmann

et al. 2021

J. Chem. Theory Comput.

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The calculation of accurate reaction energies and barrier heights is essential in computational studies of reaction mechanisms and thermochemistry. To assess methods regarding their ability to predict these two properties, high-quality benchmark sets are required that comprise a reasonably large and diverse set of organic reactions. Due to the time-consuming nature of both locating transition states and computing accurate reference energies for reactions involving large molecules, previous benchmark sets have been limited in scope, the number of reactions considered, and the size of the reactant and product molecules. Recent advances in coupled-cluster theory, in particular local correlation methods like DLPNO-CCSD(T), now allow the calculation of reaction energies and barrier heights for relatively large systems. In this work, we present a comprehensive and diverse benchmark set of barrier heights and reaction energies based on DLPNO-CCSD(T)/CBS called BH9. BH9 comprises 449 chemical reactions belonging to nine types common in organic chemistry and biochemistry. We examine the accuracy of DLPNO-CCSD(T) vis-a-vis canonical CCSD(T) for a subset of BH9 and conclude that, although there is a penalty in using the DLPNO approximation, the reference data are accurate enough to serve as a benchmark for density functional theory (DFT) methods. We then present two applications of the BH9 set. First, we examine the performance of several density functional approximations commonly used in thermochemical and mechanistic studies. Second, we assess our basis set incompleteness potentials regarding their ability to mitigate basis set incompleteness errors. The number of data points, the diversity of the reactions considered, and the relatively large size of the reactant molecules make BH9 the most comprehensive thermochemical benchmark set to date and a useful tool for the development and assessment of computational methods.

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Section: Design Of Bh9 and Computational Detailsmentioning

confidence: 99%

BH9, a New Comprehensive Benchmark Data Set for Barrier Heights and Reaction Energies: Assessment of Density Functional Approximations and Basis Set Incompleteness Potentials

Prasad

Pei

Edelmann

et al. 2021

J. Chem. Theory Comput.

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“…[2,3]‐Sigmatropic rearrangements, also called Wittig rearrangements, involves a 1,3‐shift of allyl ethers to deliver allylic alcohols [57] . Not until 2019 has the use of the Evans’ oxazolidinone auxiliaries for such [2,3]‐sigmatropic rearrangements been achieved by Collum and coworkers [58] . During the investigation, metal enolates 56 generated from Li, Na and Ti were tried, leading to the deacylation product 57 without Wittig rearrangements (Scheme 14a), while boron enolates Int‐4 generated from n ‐Bu 2 BOTf and Et 3 N, chelated by the alkoxy moiety rather than the carbonyl of oxazolidinone, rearranged to give syn products 58 in good yields and high selectivities, which was in accordance with the common Evans’ boron‐based aldol reactions (Scheme 14b) [7a] …”

Section: Extension Of Evans’ Chiral Auxiliary‐based Asymmetric Synthe...mentioning

confidence: 99%

Evans’ Chiral Auxiliary‐Based Asymmetric Synthetic Methodology and Its Modern Extensions

Chen,

Huang

2023

Eur J Org Chem

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Although the asymmetric catalysis has made a spurt of progress, the use of chiral auxiliaries remains crucial in asymmetric synthesis due to both the reliability and versatility of the methods, and the predictability of stereochemistry of the reactions. Up to date, Evans’ chiral non‐racemic oxazolidinone‐based asymmetric synthetic methodology is still widely used in asymmetric synthesis. More importantly, the Evans asymmetric synthetic methodology turned out to be a fruitful source of inspiration for the development of related asymmetric synthetic methodologies. However, although reviews on the application of Evans’ asymmetric synthetic methodology in both organic synthesis and medicinal chemistry continually to appear in the literature, a comprehensive review dedicating to the extensions of Evans’ chiral non‐racemic oxazolidinone‐based asymmetric methodology remains elusive. In this review, we summarize the extensions of the Evans asymmetric methodology, which cover: (1) the modification of the chiral oxazolidinone auxiliaries; (2) the extension of the Evans’ asymmetric aldol reaction from Evans’ syn‐aldol to other diastereomeric aldol adducts; (3) the extension of the asymmetric reaction types; (4) the extension of chiral imide‐type substrates to N‐alkenyl, N‐allenenyl and N‐alkynyl oxazolidinones; (5) the achiral oxazolidinone‐based asymmetric catalysis; (6) the catalytic transformation of Evans’ products; and (7) the straightforward transformations of Evans’ chiral products to other classes of compounds than the chiral carboxylic acids, esters, alcohols, and Weinreb amides.

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“…The early study on the asymmetric reduction of α-oxobutyrolactones was achieved by utilizing the biocatalysis, , transition-metal Rh, − and Ru catalyst, and the substrates were limited in ketopantoyl lactone and dihydrofuran-2,3-dione. Therefore, developing an effective method for the construction of various chiral α-hydroxybutyrolactones is highly desirable in organic synthetic chemistry …”

mentioning

confidence: 99%

Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of β-Substituted α-Oxobutyrolactones

Li²,

Liu³

et al. 2021

J. Org. Chem.

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A concise and effective ruthenium-catalyzed asymmetric transfer hydrogenation of β-substituted α-oxobutyrolactones has been developed, delivering a series of cis-β-substituted α-hydroxybutyrolactone derivatives with excellent yields, enantioselectivities, and diastereoselectivities. Two consecutive stereogenic centers were constructed in one step through dynamic kinetic resolution under basic conditions. The reaction could be conducted on a gram scale without loss of activity and enantioselectivity. The reductive products could be easily transformed into useful building blocks.

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Wittig Rearrangements of Boron-Based Oxazolidinone Enolates

Cited by 7 publications

References 36 publications

BH9, a New Comprehensive Benchmark Data Set for Barrier Heights and Reaction Energies: Assessment of Density Functional Approximations and Basis Set Incompleteness Potentials

BH9, a New Comprehensive Benchmark Data Set for Barrier Heights and Reaction Energies: Assessment of Density Functional Approximations and Basis Set Incompleteness Potentials

Evans’ Chiral Auxiliary‐Based Asymmetric Synthetic Methodology and Its Modern Extensions

Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of β-Substituted α-Oxobutyrolactones

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