Tosylhydrazones, with methyllithium

Camphor tosylhydrazone, with methyllithium to give 2-bor-nene, 51, 66... 

Tosylhydrazones, with methyllithium to give olefins, 51, 69 Trialkyloxonium salts, as alkylating agents, 51,144... 

Methylcyclohexene, from 2-methyl-cyclohexanone tosylhydrazone and methyllithium, 51,69 Methylenecyclopropanes, 50,30 Methyl iodide, with triphenyl phosphite and cyclohexanol, 51,45 with triphenyl phosphite and neopentyl alcohol, 51,44 METHYL ftrans-2-IODO-l-TETRA-LIN)CARBAMATE, 51,112 Methyl (frans-2-iodo-l-tetralin)carba-mate, with potassium hydroxide to give 1,2,3,4-tetrahydronaph-thalene(l,2)imine, 51,53 Methyllithium, with camphor tosylhydrazone to give 2-bomene, 51, 66... 

The dry tosylhydrazone (20 g, 45.5 mmol) is dissolved in 750 ml of 1,2-dimethoxyethane (freshly distilled from lithium aluminum hydride) in a flame-dried 1 liter round bottom flask fitted with a 240 ml addition funnel, a drierite tube and a magnetic stirrer. A 2.05 M ether solution of methyllithium (130 ml, Alfa Inorganics, Inc.—Caution to avoid the mineral oil impurity the methyllithium solution is decanted from a cold solution which contains a precipitate) is placed in the dropping funnel and added over a 60 min period. The temperature of the reaction mixture increases to ca. 35° during the addition however, no cooling precautions are required. The highly colored reaction mixture is stirred for 7 hr and then poured into 1.5 liters of ice water. The flocculent precipitate is digested for 12 hr at room temperature to speed the filtration. After filtration the filter cake is washed with 500 ml water and dried under vacuum at 50° for several hr. The androsta-5,16-dien-3l5-ol is obtained in ca. 70% yield after recrystallization from methanol mp 138-139°. 

The 1,2-carbonyl transposition takes place through the enJo-epoxide 18 easily prepared through the tosylhydrazone 16, followed by regioselective cleavage to the less substituted double bond (17) with 2 equivalents of methyllithium [4] and epoxidation with MCPBA in chloroform from the more accesible convex face of the decalin system. 

In the case of verbenone tosylhydrazone (117), 8-pinene (118) is produced along with verbenene (119) following methyllithium treatment (equation 17). ... 

After reprotection of the lactol, the resulting pentacyclic keto alcohol (271), was transformed into the corresponding tosylhydrazone, which was treated with excess methyllithium to give rise to olefin (272). 

Similarly, when an aldehyde or ketone is treated with p-toluenesulfonylhydrazine (P-CH3C6H4NHNH2), a p-toluenesulfonylhydrazone (tosylhydrazone) (Scheme 9.69) is formed. Now, when this stable, easily purified carbonyl derivative is treated with at least two equivalents of a strong base (such as methyllithium, CH3Li),proton loss on the carbon adjacent to the xp -hybridized center (i.e., the a-carbon) occurs and an organolithiated alkene results. Hydrolysis of the latter results in alkene formation and the consummation of the Shapiro reaction. ... 

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