Synlett 2013; 24(13): 1737-1738
DOI: 10.1055/s-0033-1338964
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© Georg Thieme Verlag Stuttgart · New York

Diiodomethane: A Versatile C1 Building Block

Cláudia Diana C. B. G. Raposo
REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal   Email: piccfa@gmail.com
› Author Affiliations
Further Information

Publication History

Publication Date:
17 July 2013 (online)

 
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Cláudia Raposo was born in Oeiras, Portugal in 1987. She received both her B.Sc. in Applied Chemistry and her M.Sc. in Bioorganic Chemistry from the Faculdade de Ciências e Tecnologia of Universidade Nova de Lisboa, Portugal, where she is currently working under the supervision of Dr. Krasimira Petrova. Her research is focused on carbohydrate synthesis and glucose-containing nanoparticles for targeted drug delivery.

Introduction

Diiodomethane, better known as methylene iodide, is a dense (3.325 g/mL at 25˚C), light-sensitive, pale-yellow liquid. Because of its high density, it is used by the gemo­logical industry to determine the density of minerals.[1] Being such an interesting compound, diiodomethane is a versatile C1 building block, which can be used to form carbon–carbon and carbon–heteroatom bonds. It is an easy-to-handle compound and can be used in a wide number of different reactions such as epoxidation,[2] diazotization,[3] iodomethylation,[4] cyclopropanation,[5] alkene reduction,[6] and sigmatropic rearrangement.[7] In the presence of metallic samarium, the air-sensitive samarium diiodide (SmI2) is formed in situ; this is cheaper than buying samarium diiodide.[8]

Diiodomethane is commercially available, but can also be prepared by mixing methylene dichloride and sodium ­iodide in dimethylformamide at a constant temperature of 100 °C for 6–8 hours.[9]


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Abstracts

(A) Alkylation of Diiodomethane

Bull and Charette reported an improved procedure to obtain functionalized gem-diiodoalkanes with acceptable functional group tolerance towards olefins, acetals, ethers, carbamates, and hindered esters.[10]

(B) β-Elimination of 2-Halogen-3-hydroxyesters and Synthesis of (Z)-Vinyl Halides

(E)-α,β-Unsaturated esters were synthesized from 2-halo-3-hydroxyesters in good to excellent yields using a mixture of metallic samarium and diiodomethane. (Z)-Vinyl halides can be obtained with high diastereoselectivities and yields from O-acetylated 1,1-diiodo alcohols, metallic samarium, and diiodomethane in THF at room temperature.[8]

(C) Synthesis of 2,3-Dideuterioesters

The 1,4-reduction of α,β-unsaturated esters with D2O in the presence of metallic samarium and diiodomethane afforded the corresponding 2,3-dideuterioesters in good to excellent yields.[6]

(D) Transformation of Carbonyl Compounds into Epoxides

Epoxides are important because they can be opened by a variety of nucleophiles to afford 1,2-difunctionalized systems. Concellón et al. reported a general, easy, and simple transformation of aldehydes and ketones into epoxides with excellent yields using diiodomethane and methyllithium at 0 °C.[2]

(E) Synthesis of (E)-α-Hydroxy-β,γ-unsaturated Amides

Concellón and co-workers[11] reported an easy and simple procedure to prepare (E)-α-hydroxy-β,γ-unsaturated amides using metallic ­samarium and diiodomethane with high regio- and diastereo­selectivity.

(F) Cyclopropanation

Cyclopropanation of alkenes can be carried out by a mixture of metallic samarium and diiodomethane.[11] Cyclopropanation of terminal alkynes under the action of diiodomethane and triethylaluminum proceeded stereoselectively.[5]

(G) Iodomethylation of Amino Aldehydes

The halomethylation of carbonyl compounds is difficult to achieve due to the instability of halomethyllithium compounds. As an alternative, Bernad et al. reported a smoothly proceeding reaction using metallic samarium and diiodomethane.[4]

(H) Double Carbonylation of Diiodomethane

Double carbonylation of diiodomethane in triethylorthoformate in the presence of catalytic amounts of rhodium complex gave diethylmalonate in good yield.[12]

(I) Sigmatropic Rearrangement

Li and co-workers described an efficient method for the synthesis of β-diketones from aromatic α-bromo ketones in the presence of di­iodomethane and diethylzinc. Aliphatic α-bromomethyl ketones gave 2,4-disubstituted furans or cyclopropanols in moderate yield.[7]

(J) Diazotization for the Synthesis of Aryl Iodides

The reactions of aryl amines in the presence of isoamyl nitrite and diiodomethane formed aryl iodides cleanly and in good yield.[3]

(K) Coupling Molecules with a CH2 Linkage

In the synthesis of ditopic ligands, bispyrazolylpyridine molecules can be coupled with CH2 linkages using sodium hydride and diiodomethane in dichloromethane with moderate yields, as reported by Zadykowicz and Potvin.[13]


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  • References

  • 1 Massi L, Fritsch E, Collins AT, Hainschwang T, Notari F. Diamond Relat. Mater. 2005; 14: 1623
  • 2 Concellón JM, Cuervo H, Fernández-Fano R. Tetrahedron 2001; 57: 8983
  • 3 Truong AP, Aubele DL, Probst GD, Neitzel ML, Semko CM, Bowers S, Dressen D, Hom RK, Konradi AW, Sham HL, Garofalo AW, Keim PS, Wu J, Dappen MS, Wong K, Golbach E, Quinn KP, Sauer J.-M, Brigham EF, Wallace W, Nguyen L, Hemphill SS, Bova MP, Basi G. Bioorg. Med. Chem. Lett. 2009; 19: 4920
  • 4 Concellón JM, Bernad PL, Pérez-Andrés JA. J. Org. Chem. 1997; 62: 8902
    • 5a Ramazanov IR, Lukýanova MP, Sharipova AZ, Ibragimov AG, Dzhemilev UM, Nefedov OM. Russ. Chem. Bull., Int. Ed. 2001; 50: 1406
    • 5b Lebel H, Marcoux J, Molinaro C, Charette AB. Chem. Rev. 2003; 103: 977
  • 6 Concellón JM, Huerta M. Tetrahedron Lett. 2002; 43: 4943
  • 7 Li L, Cai P, Xu D, Guo Q, Xue S. J. Org. Chem. 2007; 72: 8131
  • 8 Concellón JM, Rodríguez-Solla H, Huerta M, Pérez-Andrés J. Eur. J. Org. Chem. 2002; 11: 1839
  • 9 Xu B., CN102020529-A, 2011.
  • 10 Bull A, Charette B. J. Org. Chem. 2008; 73: 8097
    • 11a Concellón JM, Bernad PL, Bardales E. Chem.–Eur. J. 2004; 10: 2445
    • 11b Mistry S., Daras E., Fromont C., Jadhav G., Fischer P. M., Kellam B., Hill S. J., Baker J. G., WO 2012/004549 A1, 2012.
  • 12 Cheong M, Kim M.-N, Shim Y. J. Organomet. Chem. 1996; 520: 253
  • 13 Zadykowicz J, Potvin PG. J. Heterocycl. Chem. 1999; 36: 623

  • References

  • 1 Massi L, Fritsch E, Collins AT, Hainschwang T, Notari F. Diamond Relat. Mater. 2005; 14: 1623
  • 2 Concellón JM, Cuervo H, Fernández-Fano R. Tetrahedron 2001; 57: 8983
  • 3 Truong AP, Aubele DL, Probst GD, Neitzel ML, Semko CM, Bowers S, Dressen D, Hom RK, Konradi AW, Sham HL, Garofalo AW, Keim PS, Wu J, Dappen MS, Wong K, Golbach E, Quinn KP, Sauer J.-M, Brigham EF, Wallace W, Nguyen L, Hemphill SS, Bova MP, Basi G. Bioorg. Med. Chem. Lett. 2009; 19: 4920
  • 4 Concellón JM, Bernad PL, Pérez-Andrés JA. J. Org. Chem. 1997; 62: 8902
    • 5a Ramazanov IR, Lukýanova MP, Sharipova AZ, Ibragimov AG, Dzhemilev UM, Nefedov OM. Russ. Chem. Bull., Int. Ed. 2001; 50: 1406
    • 5b Lebel H, Marcoux J, Molinaro C, Charette AB. Chem. Rev. 2003; 103: 977
  • 6 Concellón JM, Huerta M. Tetrahedron Lett. 2002; 43: 4943
  • 7 Li L, Cai P, Xu D, Guo Q, Xue S. J. Org. Chem. 2007; 72: 8131
  • 8 Concellón JM, Rodríguez-Solla H, Huerta M, Pérez-Andrés J. Eur. J. Org. Chem. 2002; 11: 1839
  • 9 Xu B., CN102020529-A, 2011.
  • 10 Bull A, Charette B. J. Org. Chem. 2008; 73: 8097
    • 11a Concellón JM, Bernad PL, Bardales E. Chem.–Eur. J. 2004; 10: 2445
    • 11b Mistry S., Daras E., Fromont C., Jadhav G., Fischer P. M., Kellam B., Hill S. J., Baker J. G., WO 2012/004549 A1, 2012.
  • 12 Cheong M, Kim M.-N, Shim Y. J. Organomet. Chem. 1996; 520: 253
  • 13 Zadykowicz J, Potvin PG. J. Heterocycl. Chem. 1999; 36: 623

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