This article summarizes the results of our recent studies on development of new reactions with samarium diiodide utilizing its characteristic reactivities. The reactions dealt in this article include novel carbon-carbon bond forming reactions of both intramolecular and intermolecular types, and functional group transformations. Also, some examples of asymmetric synthesis by intermolecular pinacol coupling reactions and hydrodimerization of α,β-unsaturated carbonyl compounds are presented here.
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1 Introduction
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2 Reactions Involving Intermolecular C-C Bond Formation
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2.1 Coupling Reaction of Isothiocyanates or Isocyanates with SmI2
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2.2 A Facile Synthesis of 4-Hydroxy-(E)-alkenoic Esters
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2.3 Highly Diastereoselective Intermolecular Pinacol Coupling Reactions
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2.4 Asymmetric Hydrodimerizations of α,β-Unsaturated Carbonyl Compounds
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2.5 A Novel C-C Bond Formation Process Mediated by SmI2: Effective Approach to Baylis-Hillman Adducts
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3 Reactions Involving Intramolecular C-C Bond Formation
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3.1 Reductive Intramolecular Cyclization of α-Bromo Silyl Ethers
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3.2 Intramolecular Reductive Cyclization of β-Ketoisothiocyanates Promoted by Samarium Diiodide
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4 Reactions Proceeding without the Formation of a C-C Bond
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4.1 Novel Reduction of Isothiocyanates to Thioformamides with SmI2
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4.2 A Convenient Coupling of Isocyanates with Tertiary Alcohols with a Catalytic Amount of SmI2
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4.3 Efficient Synthesis of Iodohydrins by Selective Cleavage of Epoxides with Samarium Iodide Complex
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4.4 Highly Regioselective Cleavages and Iodinations of Cyclic Ethers with SmI2
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4.5 Facile Synthesis of Enol Ethers by Cleavage of α-Bromoacetals and α-Bromoketals Mediated by SmI2
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5 Conclusion
samarium diiodide - organometallic reagents - electron transfer - reduction - radical reactions - intramolecular cyclization
