Asmic

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Asmic
Asmic.png
Asmic Crystals.png
Names
Preferred IUPAC name
1-[(Isocyanomethyl)sulfanyl]-2-methoxybenzene
Other names
Asmic; Anisyl sulfanyl methyl isocyanide
Identifiers
3D model (JSmol)
  • InChI=1S/C9H9NOS/c1-10-7-12-9-6-4-3-5-8(9)11-2/h3-6H,7H2,2H3
    Key: JNVYKHCAQCKTBG-UHFFFAOYSA-N
  • COC1=CC=CC=C1SC[N+]#[C-]
Properties
C9H9NOS
Molar mass 179.24 g·mol−1
Appearance Off-white solid
Melting point 27 °C (81 °F; 300 K)
Solubility in polar organic solvents Soluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Anisyl sulfanyl methyl isocyanide (Asmic)[1][2] is an organic molecule that contains an isocyanide group and an ortho-methoxy-phenyl sulfide group. Asmic can be used to synthesize tri-substituted isocyanides. Asmic is a colorless to off-white solid with a melting point of 27 °C[3] that can be prepared by dehydration of the corresponding formamide by POCl3.[4][5]

Asmic can be deprotonated at the position adjacent to the isocyanide by various organic bases. The anionic form of Asmic, which is stable at low temperatures, can be alkylated with a variety of electrophiles. Two sequential deprotonation-alkylation reactions and a subsequent sulfur-lithium exchange reaction allow the synthesis of tri-substituted isocyanides.[4]

The ortho-methoxy-phenyl sulfide group is thought to facilitate deprotonation by chelating to metalated bases allowing for the base to achieve optimal trajectory during the deprotonation.[4]

Asmic can be used to prepare oxazoles by condensation reactions with esters. The ortho-methoxy-phenyl sulfide group can also undergo sulfur-lithium exchange, and likely proceeds via a 10-s-3 sulfuranide.

References[edit]

  1. ^ Fleming, F. F. Composition, Synthesis, and Use of Isonitriles. U.S. Patent 8,269,032, Sept 18, 2012.
  2. ^ Zhu, Jieping; Tron, Gian Cesare; Novellino, Ettore; Massarotti, Alberto; Mercalli, Valentina; Basso, Andrea; Giustiniano, Mariateresa (2017-03-06). "To each his own: isonitriles for all flavors. Functionalized isocyanides as valuable tools in organic synthesis". Chemical Society Reviews. 46 (5): 1295–1357. doi:10.1039/C6CS00444J. ISSN 1460-4744. PMID 27983738.
  3. ^ Abstracts of Papers, 256th ACS National Meeting & Exposition, Boston, MA, United States, August 19-23, 2018 ASMIC-driven synthesis of vinyl isocyanide
  4. ^ a b c Alwedi, Embarek; Lujan-Montelongo, J. Armando; Pitta, Bhaskar R.; Chao, Allen; Cortés-Mejía, Rodrigo; del Campo, Jorge M.; Fleming, Fraser F. (2018-09-21). "Asmic: An Exceptional Building Block for Isocyanide Alkylations". Organic Letters. 20 (18): 5910–5913. doi:10.1021/acs.orglett.8b02574. PMC 6172042. PMID 30188137.
  5. ^ Shenvi, Ryan A.; Schnermann, Martin J. (2015-03-25). "Syntheses and biological studies of marine terpenoids derived from inorganic cyanide". Natural Product Reports. 32 (4): 543–577. doi:10.1039/C4NP00109E. PMC 4414506. PMID 25514696.