1001080-26-7

Basic information

• Product Name: 6-aza-5-(trimethylsilylethyl)-9,9-dimethyl-2-(p-toluenesulfonyl)-8-oxabicyclo[4.3.0]non-1-en-7-one
• CAS NO: 1001080-26-7
• Molecular Weight: 421.633
• Mol File: 1001080-26-7.mol
• Article Data: 1

Chemical Properties

• CAS DataBase Reference: 6-aza-5-(trimethylsilylethyl)-9,9-dimethyl-2-(p-toluenesulfonyl)-8-oxabicyclo[4.3.0]non-1-en-7-one(CAS DataBase Reference)
• NIST Chemistry Reference: 6-aza-5-(trimethylsilylethyl)-9,9-dimethyl-2-(p-toluenesulfonyl)-8-oxabicyclo[4.3.0]non-1-en-7-one(1001080-26-7)
• EPA Substance Registry System: 6-aza-5-(trimethylsilylethyl)-9,9-dimethyl-2-(p-toluenesulfonyl)-8-oxabicyclo[4.3.0]non-1-en-7-one(1001080-26-7)

Safety Data

• Hazardous Substances Data: 1001080-26-7(Hazardous Substances Data)

Upstream product

• 763-13-3 but-3-en-1-yltrimethylsilane 
• 192136-96-2 5,5-dimethyl-3-p-toluenesulfonyl-4-vinylideneoxazolidin-2-one 

Relevant articles and documents

Chameleon reactivity of the allene bond of 4-vinylidene-2-oxazolidinone: Novel through-space conjugative nucleophilic addition of electron-rich alkenes and hetero-nucleophiles

The Cα=Cβ double bond of aliene carbamates 1 serves as an electron acceptor similar to the double bond of conjugated enones by means of a through-space interaction with the N-SO2 bond; the carbamate double bond is thus subject to nucleophilic addition for a wide variety of nucleophiles, which proceeds under mild conditions by heating at 70-100°C. Depending on the kind of nucleophiles, 1 displays three different reaction modes: 1) Typically enol ethers and allylsilanes promote 1,3-sulfonyl migration of 1 and undergo the inverse electron demand Diels-Alder reaction with the 1-aza-1,3-butadiene intermediates II thus formed to furnish bicyclic 2-alkoxy-5-sulfonyltetrahydropyridines 2 and 2-silylmethyl-5- sulfonyltetrahydropyridines 3, respectively, with high regio- and stereoselectivity and retention of configuration of the double bonds of these electron-rich alkenes; 2) silanes (RnSiH4-n, n = 1-3) and thiols deliver the hydride and the thiolate at the Cβ carbon and promote the 1,3-sulfonyl migration, followed by protonation of the thus-formed carbamate anion (Z)-III to provide, for example, (Z)-4a and (Z)-4j, respectively; 3) alcohols simply add to the Cα=Cβ double bond and provide (E)-6. Usually, the reaction with alcohols is accompanied by the second pathway, giving rise to, for example, (Z)-4b in addition to (E)-6b. Phenol engages in the third pathway and provides (E)-6g exclusively. Heteroaromatics, such as furans and benzofurans follow the first pathway, however, in a different regioselectivity from enol ethers and allylsilanes, delivering the oxygen atom at the 3-position of 5-sulfonyltetrahydropyridines (2g and 2h). Indoles, on the other hand, show a dichotomy, equally enjoying the first and the third pathways and provide mixtures of (E)-7 and (E)-8, respectively.