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Alternate Names: TMS-I; TMSI; trimethylsilyl iodide.
Physical Data: bp 106-109 °C; d 1.406 g cm-3; n20D 1.4710; fp -31 °C.
Solubility: sol CCl4, CHCl3, CH2Cl2, ClCH2CH2Cl, MeCN, PhMe, hexanes; reactive with THF (ethers), alcohols, and EtOAc (esters).
Form Supplied in: clear colorless liquid, packaged in ampules, stabilized with copper; widely available.
Analysis of Reagent Purity: easily characterized by 1H, 13C, or 29Si NMR spectroscopy.
Several other methods for in situ generation of the reagent have been described.5,6 It should be noted, however, that the reactivity of in situ generated reagent appears to depend upon the method of preparation.
Handling, Storage, and Precautions: extremely sensitive to light, air, and moisture, it fumes in air due to hydrolysis (HI), and becomes discolored upon prolonged storage due to generation of I2. It is flammable and should be stored under N2 with a small piece of copper wire. It should be handled in a well ventilated fume hood and contact with eyes and skin should be avoided.
Use as a Nucleophilic Reagent in Bond Cleavage Reactions.
Phosphonate and phosphate esters are cleaved even more readily with TMS-I than carboxylic esters. The reaction of phosphonate esters proceeds via the silyl ester, which is subsequently hydrolyzed with MeOH or H2O (eq 14).
Ketones can be converted to the corresponding vinyl phosphates which react with TMS-I (3 equiv) at rt to afford vinyl iodides (eq 15).
Halogen exchange can be accomplished with reactive alkyl halides, such as Benzyl Chloride or Benzyl Bromide, and even with certain alkyl fluorides, by using TMS-I in the presence of (n-Bu)4NCl as catalyst (eq 17).
Use of TMS-I in Nucleophilic Addition Reactions.
a-Iodo trimethylsilyl ethers are produced in the reaction of aldehydes and TMS-I (eq 18). These compounds may react further to provide the diiodo derivative or may be used in subsequent synthesis.
b-Iodo ketones have been produced from reactions of TMS-I and ketones with a-hydrogens.38 This reaction presumably involves a TMS-I catalyzed aldol reaction followed by 1,4-addition of iodide.
Use of TMS-I as a Silylating Agent.
Selective and high yielding iodination and bromination of lactams occurs with Iodine or Bromine, respectively, in the presence of TMS-I and a tertiary amine base (eq 24). The proposed reaction mechanism involves intermediacy of the silyl imino ether.
TMS-I has seen limited use in the silylation of carbanions, with different regioselectivity compared to other silylating reagents in the example provided in eq 25.
A Heck-type reaction of TMS-I with alkenes in the presence of Pd0 and Et3N affords alkenyltrimethylsilanes (eq 26).
Oxidative addition of TMS-I to alkynes can also be accomplished with a three-component coupling reaction to provide the enyne product (eq 27).
Use of TMS-I as a Lewis Acid.
TMS-I used in conjunction with (MeO)4Si is an effective catalyst for acetal formation (eq 28).
Catalyst for a-Alkoxymethylation of Ketones.
Catalyst for Reactions of Acetals with Silyl Enol Ethers and Allylsilanes.
Use of TMS-I as a Reducing Agent.
Carbonyl compounds containing a-hydroxy, a-acetoxy, or a-halo groups react with excess TMS-I to give the parent ketone. a-Hydroxy ketone reductions proceed via the iodide, which is then reduced with iodide ion to form the parent ketone (eq 32).
Phosphine oxides react with TMS-I to form stable adducts (eq 36). These O-silylated products can undergo further thermolytic reactions such as alkyl group cleavage.
Oximes are activated for dehydration (aldoximes, with hexamethylsilazane) or Beckmann rearrangement (ketoximes) with TMS-I (eq 37).
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