Construction of Ge-Stereogenic Center by Desymmetric Carbene Insertion of Dihydrogermanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5643 - 5649

Published: Feb. 8, 2024

We developed a method for the enantioselective synthesis of germanium-stereogenic compounds by desymmetric carbene insertion dihydrogermanes. A chiral rhodium phosphate catalyst decomposes diaryldiazo-methanes to generate carbenes that insert enantioselectively into one two Ge–H bonds dihydrogermanes form under mild reaction conditions. By this method, variety germanes with centers were synthesized in high yields and excellent enantioselectivities. Kinetic studies showed diazo decomposition process was rate-determining step. The remaining bond germane products provides possibility preparing tetra-substituted compounds.

Language: Английский

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Allylgermane synthesis via facile and general nickela-electrocatalyzed electrophile coupling

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101257 - 101257

Published: Feb. 1, 2025

Language: Английский

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The current utility and future potential of multiborylated alkanes

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 26, 2024

Language: Английский

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Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for preparation enantioenriched ogranogermanes organosilanes, featuring broad substrate scope, mild reaction conditions, excellent enantioselectivity, low catalyst loading. The key to tolerance is use SPSiBox ligands bearing flexible tunable chiral pocket. Preliminary mechanistic studies computational unveiled origin induction ligands, mechanism insertion. not only new construction trifluoromethyl-containing molecules but also opens avenue Si- Ge-containing functional molecules.

Language: Английский

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Electrochemistry-Enabled C-Heteroatom Bond Formation of Alkyl Germanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21257 - 21263

Published: July 26, 2024

Because of their robustness and orthogonal reactivity features, alkyl germanes bear significant potential as functional handles for the construction C(sp3)-rich scaffolds, especially in context modular synthetic approaches. However, to date, only radical-based has been accessible from these handles, which limits types possible decorations. Here, we describe first general C(sp3)–heteroatom bond formation (−GeEt3) by leveraging electrochemistry unlock polar reactivity. This approach allowed us couple C(sp3)–GeEt3 with a variety nucleophiles construct ethers, esters, amines, amides, sulfonamides, sulfides, well C–P, C–F, C–C bonds. The compatibility electrochemical strategy C1 motif was also showcased, involving sequential functionalization Cl, Bpin, ultimately GeEt3 via electrochemistry.

Language: Английский

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Visible‐Light‐Driven Germyl Radical Generation via EDA‐Catalyzed ET–HAT Process

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(41)

Published: May 8, 2024

Abstract We have established a facile and efficient protocol for the generation of germyl radicals by employing photo‐excited electron transfer (ET) in an donor‐acceptor (EDA) complex to drive hydrogen‐atom (HAT) from hydride (R 3 GeH). Using catalytic amount EDA commercially available thiol benzophenone derivatives, ET‐HAT cycle smoothly proceeds simply upon blue‐light irradiation without any transition metal or photocatalyst. This also affords silyl radical hydride.

Language: Английский

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Diverse Functionality of Molecular Germanium: Emerging Opportunities as Catalysts

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24209 - 24232

Published: Aug. 22, 2024

Fundamental research on germanium as the central element in compounds for bond activation chemistry and catalysis has achieved significant feats over last two decades. Designing strategies small molecule activations ultimate catalysts established capitalize orbital modalities of germanium, apparently imitating transition-metal frontier orbitals. There is a growing body examples contemporary implicating tunability orbitals through avant-garde approaches such geometric constrained empowered reactivity, bimetallic complementarity, cooperative etc. The goal this Perspective to provide readers with an overview emerging opportunities field germanium-based by perceiving underlying key principles. This will help convert discrete set findings into more systematic vision catalyst designs. Critical exposition germanium's participations evokes challenges involved innovative designs, wherein viewpoints are provided. We close addressing forward-looking directions catalytic manifold development. hope that be motivational applied constituent pragmatic catalysts.

Language: Английский

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Facile access to allylgermanes via nickela-electrocatalyzed germylative allylation

Chem Catalysis, Journal Year: 2025, Volume and Issue: 5(4), P. 101360 - 101360

Published: April 1, 2025

Language: Английский

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Photocatalytic Germylation via Direct Hydrogen Atom Transfer

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Comprehensive Summary An innovative visible‐light‐driven direct hydrogen atom transfer ( d ‐HAT) of Ge–H bond has been developed, wherein the photoexcited 9,10‐phenanthraquinone PC HAT 9 ) serves as an efficient photocatalyst for generation germanium‐centered radicals from germanium hydrides including Ph 3 GeH, n Bu and 2 GeH . By employing hypervalent iodine reagents SOMOphiles, this protocol facilitates streamlined germylation through a mechanism involving germyl radical addition followed by β‐cleavage carboxyl to yield diverse array ethynyl‐, vinyl‐, nitrile‐, phenyl‐functionalized germanes. The methodological leap signifies noteworthy departure previous photocatalytic indirect i relying on combined usage SET with abstractors, which not only advances methodology creating in fashion but also provides access structurally novel pharmaceutically promising organogermanium compounds that are difficult synthesize routine methods.

Language: Английский

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Synthesis of chiral germanium center enabled by poly-deborylative alkylation and desymmetrization

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: May 30, 2025

Chiral germanium centers are historically undervalued due to their extremely limited synthetic accessibility. Although shares similar chemical properties with silicon, synthesizing chiral proves significantly more challenging. To facilitate rapid access centers, we develop two strategies: deborylative alkylation of chlorides and copper-catalyzed diol desymmetrization. The α-boryl carbanion is demonstrated be an exceptional coupling partner for chloride, yielding 1,3-prochiral diols, which subsequently undergo desymmetrization afford centers. By combining these methodologies, successfully transform simple tetrachloride into a center in merely four steps, representing significant advancement main-group element chirality. Additionally, this strategy efficiently facilitates the construction silicon-stereogenic as well. Subsequent deoxygenative cross-coupling reactions products further expand scope organogermanium chemistry, revealing entirely new possibilities.

Language: Английский

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