Migration of the double bond

Step 2 Enzyme catalyzed proton transfer steps cause migration of the double bond converting the mine formed m step 1 to an isomeric mine... 

Conjugate acid (Section 1 13) The species formed from a Brpnsted base after it has accepted a proton Conjugate addition (Sections 1010 and 1812) Addition reaction in which the reagent adds to the termini of the con jugated system with migration of the double bond synony mous with 1 4 addition The most common examples include conjugate addition to 1 3 dienes and to a 3 unsaturated car bonyl compounds... 

Medroxyprogesterone acetate (74) is stmcturaHy related to and has been prepared from hydroxyprogesterone (39) (Fig. 10). Formation of the bis-ketal accomplishes the protection of the ketones and the required migration of the double bond. Epoxidation with peracetic acid produces a mixture of epoxides (75), with a predominating. Treatment of the a-epoxide with methyl magnesium bromide results in diaxial opening of the epoxide. Deprotection of the ketones provides (76), which is dehydrated to (77) by treatment with dilute sodium hydroxide in pyridine. Upon treatment with gaseous hydrochloric... 

In a synthesis of sativene a carbonyl group was protected as a 2,4-DNP while a double bond was hydrated with BH3/H202/0H . Attempted protection of the carbonyl group as a ketal caused migration of the double bond protection as an oxime or oxime acetate was unsatisfactory since they would be reduced with BH3. 

Displacement of an allylic halide is complicated by side reactions involving migration of the double bond. A good example is the reaction of 7a-bromo-3 -acetoxy-A -steroids (201) which gives, besides the expected... 

Pregnenolone is transported from the mitochondria to the ER, where a hydroxyl oxidation and migration of the double bond yield progesterone. Pregnenolone synthesis in the adrenal cortex is activated by adrenocorticotropic hormone (ACTH), a peptide of 39 amino acid residues secreted by the anterior pituitary gland. 

With respect to the olefinic substrate, various functional groups are tolerated, e.g. ester, ether, carboxy or cyano groups. Primary and secondary allylic alcohols, e.g. 14, react with concomitant migration of the double bond, to give an enol derivative, which then tautomerizes to the corresponding aldehyde (e.g. 15) or ketone ... 

Migration of the double bond from an exocyclic 5-position to an endo-cyclic 4-position occurred on treatment of the 4-mesylate of the 5-enoside (15) with lithium aluminum hydride in ether (22). The structure of... 

The addition, therefore, follows Markovnikov s rule. Primary alcohols give better results than secondary, and tertiary alcohols are very inactive. This is a convenient method for the preparation of tertiary ethers by the use of a suitable alkene such as Me2C=CH2. Alcohols add intramolecularly to alkenes to generate cyclic ethers, often bearing a hydroxyl unit as well. This addition can be promoted by a palladium catalyst, with migration of the double bond in the final product. Rhenium compounds also facilitate this cyclization reaction to form functionalized tetrahydrofurans. 

Each of these procedures for epoxidation and ring opening is the equivalent of an allylic oxidation of a double bond with migration of the double bond. 

The difficulty in controlling the regiochemistry during radical-denitration of allylic nitro compounds is well known. The migration of the double bond is a serious problem, as shown in Eq. 7.96. This problem is overcome by a hydride transfer reaction in the presence of a palladium catalyst (Eq. 7.97).140... 

Another leading research theme was the migration of the double bond, for example, in the saponification of an allyl nitrile to crotonic acid. 36... 

Under the conditions which cause migration of the double bonds, e.g. treatment with sodium and especially potassium, the isolated double bonds can become conjugated, and thus they undergo reduction by metals. Some macrocyclic cycloalkadienes were reduced (predominently to trans cycloalkenes) by treatment with potassium on alumina in a hydrogen atmosphere [350]. 

Hosokawa, Murahashi, and coworkers demonstrated the ability of Pd" to catalyze the oxidative conjugate addition of amide and carbamate nucleophiles to electron-deficient alkenes (Eq. 42) [177]. Approximately 10 years later, Stahl and coworkers discovered that Pd-catalyzed oxidative amination of styrene proceeds with either Markovnikov or anti-Markovnikov regioselectivity. The preferred isomer is dictated by the presence or absence of a Bronsted base (e.g., triethylamine or acetate), respectively (Scheme 12) [178,179]. Both of these reaction classes employ O2 as the stoichiometric oxidant, but optimal conditions include a copper cocatalyst. More recently, Stahl and coworkers found that the oxidative amination of unactivated alkyl olefins proceeds most effectively in the absence of a copper cocatalyst (Eq. 43) [180]. In the presence of 5mol% CUCI2, significant alkene amination is observed, but the product consists of a complicated isomeric mixture arising from migration of the double bond into thermodynamically more stable internal positions. 

Treatment of tri-O-acetyl-D-glucal with boiling water results in the migration of the double bond to the 2,3-positions and the elimination... 

Bishop and Hamer found that acyclic a,/8-unsaturated 1,2-diketones form cyclopentanol derivatives in high yield, while / ,y-unsaturated derivatives form oxetanes by internal cycloaddition.114 Unexpectedly, the y,S-unsatu-rated derivatives also gave oxetanes after an initial migration of the double bond to the /8,y position. The formation of oxetanes such as 38 was observed in the camphorquinone sensitized dimerization of butadiene.115 Photocycloadditions of a-diketones to various olefins have been studied by several groups.116... 

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