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Related Experiment Video

Updated: Jun 7, 2026

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

Published on: February 6, 2019

SmI2-mediated radical cyclizations directed by a C-Si bond.

Hassan Y Harb¹, Karl D Collins, Jose V Garcia Altur

¹School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom.

Organic Letters

|November 6, 2010

Summary

Silicon stereocontrol elements in samarium diiodide (SmI2) mediated cyclizations yield highly diastereoselective cyclobutanols and cyclopentanols. This method offers a versatile C-Si bond for further chemical transformations.

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Area of Science:

Organic Chemistry
Stereoselective Synthesis
Organometallic Chemistry

Background:

Cyclization reactions are fundamental in organic synthesis for constructing cyclic molecules.
Achieving high diastereoselectivity in cyclizations remains a significant challenge.
Samarium diiodide (SmI2) is a powerful reducing agent used in various organic transformations.

Purpose of the Study:

To develop a stereoselective method for cyclobutanol and cyclopentanol synthesis.
To investigate the utility of silicon as a stereocontrol element in SmI2-mediated cyclizations.
To establish an asymmetric route for preparing cyclization substrates.

Main Methods:

SmI2-mediated cyclization reactions utilizing silicon stereocontrol elements.
Copper-catalyzed silyl transfer reactions for asymmetric substrate synthesis.

Main Results:

Excellent diastereocontrol was achieved in cyclobutanol and cyclopentanol formation.
The C-Si bond in the cyclized products served as a versatile handle for further synthetic modifications.
An efficient asymmetric route to the cyclization substrates was successfully developed.

Conclusions:

Silicon-based stereocontrol elements are highly effective in SmI2-mediated cyclizations.
The developed methodology provides access to diastereomerically enriched cyclic alcohols.
The synthetic strategy offers a valuable tool for complex molecule synthesis.