Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent.

Area of Science:

• Organic Chemistry
• Synthetic Methodology
• Hypervalent Iodine Chemistry

Background:

• Organic nitrates are crucial in pharmaceuticals, energetic materials, and synthesis.
• Efficient and direct synthesis of organic nitrates is limited by a lack of powerful nitrooxylating reagents.
• Existing methods often require harsh conditions or lack broad applicability.

Purpose of the Study:

• To develop novel, stable, and highly reactive nitrooxylating reagents.
• To establish mild and operationally simple protocols for synthesizing diverse organic nitrates.
• To demonstrate the utility of these reagents in challenging transformations like regioselective nitrooxylation and direct C-H functionalization.

Main Methods:

• Synthesis of oxybis(aryl-λ³-iodanediyl) dinitrates (OAIDNs) from aryliodine diacetate and nitric acid.
• Application of OAIDNs for zinc-catalyzed regioselective nitrooxylation of cyclopropyl silyl ethers.
• Direct, catalyst-free nitrooxylation of enolizable C-H bonds using OAIDNs.

Main Results:

• Bench-stable and highly reactive OAIDNs were successfully prepared.
• A mild protocol for synthesizing diverse organic nitrates was established.
• Efficient synthesis of β-nitrooxy ketones from cyclopropyl silyl ethers and direct nitrooxylation of C-H bonds were achieved with high functional-group tolerance.

Conclusions:

• OAIDNs represent a powerful new class of nitrooxylating reagents.
• The developed methods offer efficient and direct access to valuable organic nitrates under mild conditions.
• This work expands the synthetic toolbox for organic nitrate preparation and functionalization.