Total Synthesis of the Allenic Macrolide (+)-Archangiumide

Sutro, Jack L.; Fürstner, Alois

doi:10.1021/jacs.3c13304

Cited by 4 publications

(2 citation statements)

References 69 publications

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“…To remedy the issue, we have recently designed a set of tripodal silanolate ligands to harness the chelate effect; − the same ligand design was independently pursued by Lee and co-workers. , Indeed, “canopy” catalysts of type 2 are more compatible with protic groups and were found to apply to a number of challenging substrates beyond the reach of parent complex 1 . At the same time, 2 and congeners are distinguished by a remarkable tolerance for Lewis basic functionality, even though they comprise an early transition metal in its highest oxidation state. ,− …”

Section: Introductionmentioning

confidence: 99%

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Molybdenum(VI) Nitrido Complexes with Tripodal Silanolate Ligands. Structure and Electronic Character of an Unsymmetrical Dimolybdenum μ-Nitrido Complex Formed by Incomplete Nitrogen Atom Transfer

Rütter,

van Gastel,

Leutzsch

et al. 2024

Inorg. Chem.

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In contrast to a tungsten nitrido complex endowed with a tripodal silanolate ligand framework, which was reported in the literature to be a dimeric species with a metallacyclic core, the corresponding molybdenum nitrides 3 are monomeric entities comprising a regular terminal nitride unit, as proven by singlecrystal X-ray diffraction (SC-XRD). Their electronic character is largely determined by the constraints imposed on the metal center by the podand ligand architecture. 95 Mo nuclear magnetic resonance (NMR) and, to a lesser extent, 14 N NMR spectroscopy allow these effects to be studied, which become particularly apparent upon comparison with the spectral data of related molybdenum nitrides comprising unrestrained silanolate, alkoxide, or amide ligands. Attempted nitrogen atom transfer from these novel terminal nitrides to [(tBuArN) 3 Mo] (Ar = 3,5dimethylphenyl) as the potential acceptor stopped at the stage of unsymmetric dimolybdenum μ-nitrido complex 13a as the first intermediate along the reaction pathway. SC-XRD, NMR, electron paramagnetic resonance, and ultraviolet−visible spectroscopy as well as magnetometry in combination with density functional theory allowed a clear picture of the geometric and electronic structure of this mixed-valent species to be drawn. 13a is formally best described as an adduct of the type [(Mo [O] ) +III −(μN) −III −(Mo [N] ) +VI ], S = 1 / 2 complex with (Mo [O] ) +III in the low-spin configuration, whereas related complexes such as [(AdS) 3 Mo−(μN)− Mo(NtBuAr) 3 ] (19; Ad = 1-adamantyl) have previously been regarded in the literature as mixed-valent Mo +IV /Mo +V species. The spin population at the two Mo centers is uneven and notably larger at the more reduced Mo [O] atom, whereas the only spin present at the (μN) bridge is derived from spin polarization.

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Section: Introductionmentioning

confidence: 99%

“… 10 At the same time, 2 and congeners are distinguished by a remarkable tolerance for Lewis basic functionality, even though they comprise an early transition metal in its highest oxidation state. 10 , 15 − 20 …”

Section: Introductionmentioning

confidence: 99%

Molybdenum(VI) Nitrido Complexes with Tripodal Silanolate Ligands. Structure and Electronic Character of an Unsymmetrical Dimolybdenum μ-Nitrido Complex Formed by Incomplete Nitrogen Atom Transfer

Rütter,

van Gastel,

Leutzsch

et al. 2024

Inorg. Chem.

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An Efficient and Scalable “Second Generation” Total Synthesis of the Marine Polyketide Limaol Endowed with Antiparasitic Activity

Hess,

Fürstner

2024

Chemistry A European J

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The cluster of four skipped exo‐methylene substituents on the “northern” wing of limaol renders this marine natural product unique in structural terms. This arguably non‐thermodynamic array gains kinetic stability by populating conformations which impede isomerization to a partly or fully conjugated polyene. This analysis suggested that the difficulties encountered in our first total synthesis had not been caused by an overly fragile character of this unusual substructure; rather, an unfavorable steric microenvironment about the spirotricyclic core was accountable. To remedy the issue, the bulky silyl ethers were replaced by acetates; this simple change allowed all problems to be addressed, the overall yield to be multiplied, and the material throughput to be increased more than eighty‐fold per run. Key‐to‐success was a gold‐catalyzed spirocyclization reaction; the reasons why a Brønsted acid cocatalyst is needed and the origin of the excellent levels of selectivity were delineated. The modified protecting group pattern also allowed for a much‐improved fragment coupling process by a reagent controlled asymmetric allylation. Finally, a new route to the “northern” sector was established by leveraging the power of asymmetric hydrogenation of a 2‐pyrone derivative. Limaol was found to combine appreciable antiparasitic activity with very modest cytotoxicity.

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Sequence [2,3]‐Sigmatropic Rearrangement: One‐Pot Synthesis of Propargyl Allenylamines

Feng,

Xie,

Huang

et al. 2024

Chin. J. Chem.

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Comprehensive SummaryAllenes, served as highly sought‐after building blocks, are an indispensable component of synthetic chemistry. Their utility in modulating the chemical, physical, and pharmaceutical properties of organic compounds make allenes a desirable choice in various applications. Here, we report a facile method for the atom‐economical synthesis of propargyl allenylamines via an underdeveloped [2,3]‐sigmatropic rearrangement. Our strategy employs easily accessible propargylamines as starting materials, which are first converted into propargyl ammonium salts, followed by a base‐promoted [2,3]‐sigmatropic rearrangement. This one‐pot, two‐step reaction proceeds in the absence of transition metals, displays a very broad scope, and does not require the introduction of the electron‐withdrawing group into the starting materials.

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Total Synthesis of the Allenic Macrolide (+)-Archangiumide

Cited by 4 publications

References 69 publications

Molybdenum(VI) Nitrido Complexes with Tripodal Silanolate Ligands. Structure and Electronic Character of an Unsymmetrical Dimolybdenum μ-Nitrido Complex Formed by Incomplete Nitrogen Atom Transfer

Molybdenum(VI) Nitrido Complexes with Tripodal Silanolate Ligands. Structure and Electronic Character of an Unsymmetrical Dimolybdenum μ-Nitrido Complex Formed by Incomplete Nitrogen Atom Transfer

An Efficient and Scalable “Second Generation” Total Synthesis of the Marine Polyketide Limaol Endowed with Antiparasitic Activity

Sequence [2,3]‐Sigmatropic Rearrangement: One‐Pot Synthesis of Propargyl Allenylamines

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