Journal article
Asmic Isocyanide-Nitrile Isomerization-Alkylations
European journal of organic chemistry, v 2019(29), pp 4644-4648
07 Aug 2019
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Anisylsulfanylmethylisocyanide, Asmic, is a versatile building block whose alkylations provide a range of substituted isocyanides. The anisylsulfanyl group plays a critical role in the sequenced deprotonation-alkylation and the subsequent sulfanyl-lithium exchange. Complexation of the anisylsulfanyl group to BuLi in the presence of TMEDA affords a lithiated isocyanide whose alkylations generate trisubstituted isocyanides. In the absence of TMEDA, BuLi triggers cyanide expulsion to afford a transient carbene; reorientation of cyanide with attack at the carbene affords a lithiated nitrile whose alkylations afford quaternary nitriles. The complexation-induced isocyanide-nitrile rearrangement is exceptionally facile, occurring within 5 min at -78 degrees C. Detailed mechanistic and computational analyses identify the importance of chelation in the bifurcating mechanism: internal chelation favors cyanide extrusion to form a carbene whereas chelating agents favor arylsulfanyl-lithium exchange to generate a lithiated isocyanide. The combined experimental and computational analyses reveal a new mechanism for isocyanide-nitrile isomerization which provides valuable insight for rapidly assembling substituted isocyanides.
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Details
- Title
- Asmic Isocyanide-Nitrile Isomerization-Alkylations
- Creators
- Embarek Alwedi - MSDJ. Armando Lujan-Montelongo - Departmento de Química; Centro de Investigación y de Estudios Avanzados (Cinvestav); Av. Instituto Politécnico Nacional 2508 Ciudad de México 07360 MéxicoRodrigo Cortes-Mejia - Departamento de Física y Química Teórica; Facultad de Química; Universidad Nacional Autónoma de México; 04510 México CDMX MéxicoJorge M. del Campo - Departamento de Física y Química Teórica; Facultad de Química; Universidad Nacional Autónoma de México; 04510 México CDMX MéxicoBilal Altundas - Drexel UniversityFraser F. Fleming - Drexel University
- Publication Details
- European journal of organic chemistry, v 2019(29), pp 4644-4648
- Publisher
- Wiley
- Number of pages
- 5
- Grant note
- IN114418 / DGAPA-UNAM; Universidad Nacional Autonoma de Mexico 2R15AI051352-04 / NIH; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA 282791; 241445 / CONACYT; Consejo Nacional de Ciencia y Tecnologia (CONACyT) Drexel University
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000477381100001
- Scopus ID
- 2-s2.0-85069676955
- Other Identifier
- 991019168730904721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Organic