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Journal ArticleDOI

Electrochemical synthesis of isocyanides

30 Sep 1991-Tetrahedron Letters (Pergamon)-Vol. 32, Iss: 40, pp 5539-5542
TL;DR: In this paper, α-mono-and -dialkyl derivatives of TOSMIC® (p=toluenesulfonyl methylisocyanide) (2, 2a-e) are electroreductively detosylated to give the parent primary and secondary alkyl and aralkyl isocyanides 3 and 3a-E.
About: This article is published in Tetrahedron Letters.The article was published on 1991-09-30. It has received 9 citations till now. The article focuses on the topics: Alkyl & Nitrile.
Citations
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Reference EntryDOI
TL;DR: TosMIC is the only commercially available sulfonylmethyl isocyanide, which can be stored at room temperature without decomposition as discussed by the authors, and it is a stable, colorless, practically odorless solid.
Abstract: TosMIC is the acronym for 4-tolylsulfonylmethyl isocyanide or tosylmethyl isocyanide. It is the best-known member of a series of about 25 sulfonyl-substituted methyl isocyanides RSO2CH2NC collected in Chart 1 (p. 426). TosMIC is a multipurpose synthetic reagent. It is by far the most versatile synthon derived from methyl isocyanide. This chapter provides a complete account of the synthetic uses of TosMIC based on a literature search closed in January 1996, and supplemented with further data available to the authors. Also included are applications of some of the more important TosMIC homologs (TosCHRNC). TosMIC is the only commercially available sulfonylmethyl isocyanide. It is a stable, colorless, practically odorless solid, which can be stored at room temperature without decomposition. Four brief review papers on the chemistry of TosMIC have appeared, in 1980, 1987, 1993, and 1995. Several reviews on the chemistry of isocyanides in general are available. An effort has been made to make this chapter as complete as possible, in coverage both by tables and by references, with respect to the immediate objective: a survey of the “Synthetic Uses of TosMIC.” Emphasis is on the primary products derived from reactions of TosMIC and related isocyanides, with limited reference to the further utilization of these products. Thus, the next section gives a complete account of reductive cyanation, the conversion of aldehydes or ketones into cyanides with the use of TosMIC, but for obvious reasons synthetic applications of the product cyanides are not treated in this chapter. One of the subsequent sections describes the application of TosMIC to the synthesis of pyrroles, including 2,3-divinylpyrroles, which are important precursors in a new synthesis of indoles. This latter transformation, made possible by the easy availability of the precursors through TosMIC chemistry, is afforded brief coverage. As a rule, reference to preliminary papers has been omitted when the same information is available from the corresponding full papers. The patent literature is covered highly selectively and is cited only when providing new and relevant information. Negative results of reactions are reported in the text or tables only when at least some relevant information is available with respect to the conditions of such unsuccessful attempts. Keywords: tosylmethyl isocyanide; 4-tosylsulfonylmethyl isocyanide; sulfonyl; methyl isocyanide; isocyanide; synthetic application; synthetic utility

54 citations

Journal ArticleDOI
TL;DR: In this article, an efficient and widely applicable reagent-free method for the synthesis of alkyl and aryl isocyanides has been established, which is based on electrochemical reduction.

14 citations

Reference EntryDOI
TL;DR: P-Tolylsulfonylmethyl isocyanide (Ptolyls-methyl) formamide and formamide (formamide) was used for elimination as discussed by the authors.
Abstract: p-Tolylsulfonylmethyl isocyanide intermediate: N-(p-tolylsulfonylmethyl)formamide solvent: One liter of petroleum ether product: p-tolylsulfonylmethyl isocyanide Keywords: elimination, dehydration; diethyl ether

6 citations

Journal ArticleDOI
TL;DR: In this paper, the reaction of excess p-tolylsulfonylmethylisocyanide (L′) is reacted with Cu(NO3)2, the mixed-valence CuICuII complex Cu2L′6(NO 3)3 (5) is precipitated, while using CuCN gives the CuI dimer Cu 2L′4(CN)2 (4).

3 citations

References
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Journal ArticleDOI
TL;DR: Saureamide aromatischer Carbonsauren, Saureamide aliphatischer carbonsaureester with einem aromatischen Substituenten am Stickstoff and Sulfonamide aromatisches Sulfonsaurer werden durch elektrolytisch erzeugtes TMA reduktiv gespalten.
Abstract: Saureamide aromatischer Carbonsauren, Saureamide aliphatischer Carbonsauren mit einem aromatischen Substituenten am Stickstoff und Sulfonamide aromatischer Sulfonsauren werden durch elektrolytisch erzeugtes TMA reduktiv gespalten. Dabei entstehen die den Carbonsauren entsprechenden primaren Alkohole; die Sulfonamide werden zu Sulfinsauren reduziert. In beiden Fallen entstehen in hohen Ausbeuten die zugehorigen Amine. — Aromatische Carbon und Sulfonsaureester werden analog in hohen Ausbeuten zu primaren Alkoholen bzw. Sulfinsauren reduziert. — Die Benzoyl- bzw. Tosylgruppe kann mit TMA schonend und in hohen Ausbeuten aus Aminosauren und Peptiden abgelost werden. Einige einfache Peptide werden nach dem neuen Verfahren aufgebaut.

102 citations

Journal ArticleDOI
TL;DR: In this article, die Spaltungsrichtung an verschiedenen substituierten Sulfonen wird untersucht und ein Reaktionsmechanismus zur Diskussion gestellt.
Abstract: Tetramethylammonium (TMA), das an der Quecksilberkathode aus dem Tetramethylammonium-Ion TMA⊕ erzeugt wird, spaltet Sulfone in hohen Ausbeuten und unter schonenden Bedingungen in Sulfinate und RH-Verbindungen. — Die Spaltungsrichtung an verschiedenen substituierten Sulfonen wird untersucht und ein Reaktionsmechanismus zur Diskussion gestellt.

70 citations

Journal ArticleDOI
TL;DR: In this paper, Dialkylated tosylmethyl isocyanides have been conveniently reduced to the corresponding hydrocarbons with lithium in liquid ammonia, which has been successfully used in the synthesis of (Z)-9-tricosene -a sex pheromone of common house fly.

12 citations