Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Oct. 30, 2023

Within the sphere of traditional Pd

Language: Английский

---

Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15850 - 15859

Published: May 28, 2024

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored comparison to transition-metal-based technologies, yet desirable when considering controlled exploration chemical space. With current drive discover next-generation therapeutics, reaction design enables strategic incorporation an sp3 carbon center, containing multiple synthetic handles for subsequent space would be highly enabling. Here, we describe photoactivation ambiphilic C1 units generate α-bimetalloid radicals using only Lewis base and light source directly activate C–I bond. Interception these transient with various SOMOphiles rapid synthesis organic scaffolds (B, Si, Ge) orthogonal activation. In-depth theoretical mechanistic studies reveal prominent role 2,6-lutidine forming photoactive charge transfer complex stabilizing situ generated iodine radicals, as well influential boron p-orbital activation/weakening This simple efficient methodology enabled expedient access functionalized 3D frameworks can further derivatized available technologies C–B C–Si

Language: Английский

---

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

---

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

---

Orthogonal sp³‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 12, 2024

Abstract In this study, a series of enantioenriched sp 3 ‐Ge/B bimetallic modules were successfully synthesized via an enantioselective copper‐catalyzed hydroboration carbagermatrane ( Ge )‐containing alkenes. Orthogonal cross‐coupling selectivity under different Pd‐catalyzed conditions was achieved in enantiospecific manner. Notably, the chiral secondary exhibited remarkable transmetallation ability prior to primary or Bpin. The effectiveness Ge/B strategy further demonstrated through development new functional small molecules with Aggregation‐Induced Emission (AIE) and Circularly Polarized Luminescence (CPL) performance. This represents first successful example synthesis alkylgermanium reagents that permit reactions.

Language: Английский

---

Photoinduced decarboxylative germylation of α-fluoroacrylic acids: Access to germylated monofluoroalkenes

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(51), P. 6556 - 6559

Published: Jan. 1, 2024

Herein, a novel strategy is presented for the photoinduced decarboxylative and dehydrogenative cross-coupling of wide range α-fluoroacrylic acids with hydrogermanes. This methodology provides an efficient robust approach producing various germylated monofluoroalkenes excellent stereoselectivity within brief photoirradiation period. The feasibility this reaction has been demonstrated through gram-scale reaction, conversion monofluoroalkenes, modification complex organic molecules.

Language: Английский

---

Toward Multi‐Functionalized Organogermaniums: Diastereoselective Transformations of Germacycles Derived from Cheletropic Reactions of Boron‐Substituted Butadienes with Ge(II) Salts

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 22, 2024

Abstract The field of organogermanium in chemistry has recently attracted attention. Thanks to the inherent features germanium (Ge), introducing Ge‐based substituents into organic frameworks enhanced bioactivity and optoelectronic properties molecules. Herein, synthesis multi‐functionalized organogermaniums using Ge(II) salts is reported. germacycles having an allylboron moiety, which derived from (4+1) cycloadditions butadienes bearing a boronic ester moiety with salts, can be applied further allylboration aldehydes perfect diastereoselectivity. obtained allylated adducts enable access π‐extended retention stereocenters.

Language: Английский

---

Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(8)

Published: Oct. 30, 2023

Abstract Within the sphere of traditional Pd 0 /Pd II cross coupling reactions, organogermanes have been historically outperformed both in terms scope and reactivity by more conventional transmetalating reagents. Subsequently, this class compounds has largely underutilized as a partner bond‐forming strategies. Most recent studies, however, shown that alternative modes activation these notoriously robust building blocks transform into most reactive site molecule—capable outcompeting other functional groups (such boronic acids, esters silanes) for C−C C–heteroatom bond formation. As result, over past few years, literature increasingly featured methodologies explore potential chemoselective orthogonal partners. Herein we highlight some advances field organogermane chemistry with respect to their synthesis applications synthetic catalytic transformations.

Language: Английский

---

Orthogonal sp³‐Ge/B Bimetallic Modules: Enantioselective Construction and Enantiospecific Cross‐Coupling

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(16)

Published: Feb. 12, 2024

Abstract In this study, a series of enantioenriched sp 3 ‐Ge/B bimetallic modules were successfully synthesized via an enantioselective copper‐catalyzed hydroboration carbagermatrane ( Ge )‐containing alkenes. Orthogonal cross‐coupling selectivity under different Pd‐catalyzed conditions was achieved in enantiospecific manner. Notably, the chiral secondary exhibited remarkable transmetallation ability prior to primary or Bpin. The effectiveness Ge/B strategy further demonstrated through development new functional small molecules with Aggregation‐Induced Emission (AIE) and Circularly Polarized Luminescence (CPL) performance. This represents first successful example synthesis alkylgermanium reagents that permit reactions.

Language: Английский

---

Germanyl triazoles as a platform for CuAAC diversification and chemoselective orthogonal cross-coupling

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 3198 - 3204

Published: Dec. 5, 2024

We report the synthesis of germanyl triazoles formed via a copper-catalysed azide-alkyne cycloaddition (CuAAC) alkynes. The reaction is often high yielding, functional group tolerant, and compatible with complex molecules. installation Ge moiety enables further diversification triazole products, including chemoselective transition metal-catalysed cross-coupling reactions using bifunctional boryl/germyl species.

Language: Английский

---