1,3-Oxidative Rearrangements of Dienols

✍ Scribed by George Majetich; Stephen Condon; Kenneth Hull; Saeed Ahmad

• Book ID: 104232795
• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 237 KB
• Volume: 30
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)80351-8

✦ Synopsis

The intramolecular addition of allylsilanes to conjugated dienones can be used to efficiently construct a wide variety of polycyclic systems.23 However, on occasion we have been unable to prepare conjugated dienones via the addition of vinylic nucleophiles to a',d-dialkyl-3-ethoxy-cycloalkenones4

For example, enone 1 proved inert to attack by vinyllithium c4) despite vigorous conditions [five equivalents of 4, refluxing THF, 30 h], and moreover acarbomethoxyvinylcuprate,5 4-chloro-2-lithio-1-butene,6 and the lithium enolate of methyl P-(dimethylamino)-propionate7 all failed to add to enones 2 or ;I (shown below). These additions failed presumably due to the modest reactivity of vinylogous esters 1-J for 1,2addition as well as steric factors.