Nonadiene

The zirconium-catalyzed cross-coupling reaction of 1,2-nonadiene (147) and triethyl-aluminum afforded alumacyclopentanes, which were subsequently hydrolyzed to give olefins such as 148 and 149 (Eq. 14.17) [76],... 

ONE-STEP HOMOLOGATION OF ACETYLENES TO ALLENES PREPARATION OF 4-HYDR0XYN0NA-1,2-DIENE (1,2-Nonadien-4-ol)... 

Acyclic and cyclic allenes are converted to alkenes at 60 °C under atmospheric pressure of hydrogen with [RhCl(PPh3)3]. 1,2-Nonadiene (26), 3-ethyl-1,2-pentadiene and 1,2-cyclotridecadiene are hydrogenated to give cts-2-nonene (27), 3-ethyl-2-pentene and cyclotridecene (cis trans = 85 15), respective-... 

Nonadiene — m-2-Nonene (17%) 3-Ethyl-l,2-pentadiene — 3-Ethyl-2-pentene(16%)... 

Figure 8.3. The half-hydrogenated state of cycle-1,2-nonadiene shown in plan as (A) a JTs structure and (B) a jrcr structure.

In the presence of CO, insertion of CO is faster than that of allenes. In the reaction of < -iodophenol (399) with 1,2-nonadiene (400) under CO pressure (20 atm) by use of DPPB as a hgand, CO insertion generates the acylpalladium 401, to which insertion of the allene occurs to give the 7r-allylpalladium intermediate 402, and nucleophilic attack of phenohc OH yields 403 in high yield [153]. 

Carbonylation of 2-iodophenol (91) in the presence of 1,2-nonadiene (95) afforded 2-(n-hexyl)-3-methylene-2,3-dihydro-4/f-l-benzopyran -one (97) in 74% yield, showing that selective attack of phenoxy group at the substituted terminus of r-allylpalladium intermediate 96 occurred. Uses of DPPB and K2CO3 were important [43]. 

The Pd(OAc)2/dppb-catalyzed cascade reaction of o-iodophenol with 1,2-nonadiene and CO starts with a CO insertion which is followed by carbopalladation of the allene and subsequently terminated by an intramolecular nucleophilic substitution to afford O-con-taining six-membered a-methylenebenzo-y-dihydropyrones (Scheme 34). ... 

Allenes react with azides across one of their C=C= bonds to give a mixture of the expected stereoisomeric 1,2,3-triazolines. For example, from 1,2-nonadiene and phenyl-and 4-bromo-phenyl azide mixtures of the two stereoisomeric cycloadducts are obtained °. Also, picryl azide adds to tetramethylallene to give 4-isopropylidene-5,5-dimethyl-1 -picryl-1,2,3-triazoline . In contrast, heating of the allenyl azides 77 at 100 °C leads to the formation of tricyclic imines, formed by loss of nitrogen from the initial cycloadducts. 

Excess methyllithium in ether added dropwise with stirring under N2 to a cooled ethereal soln. l,l-dibromo-2-hexylcyclopropane, and allowed to warm to room temp. 1,2-nonadiene. Y 81%. F. e., also with butyllithium, s. W. R. Moore and H. R. Ward, J. Org. Ghem. 27, 4179 (1962) s. a. L. Skattebol, Acta Ghem. Scand. 17, 1683 (1963). 

---