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47.1.1.4.1 Method 1: Synthesis by Methylenation with (μ-Chloro)bis(η5-cyclopentadienyl)(dimethylaluminum)(μ-methylene)titanium (The Tebbe Reagent)

DOI: 10.1055/sos-SD-047-00100

Petasis, N. A.Science of Synthesis, (201047162.

The methylenation of carbonyl compounds is a very useful method for the synthesis of terminal alkenes. By combining this process with subsequent reactions of the alkene products it is also a practical means for a one-carbon homologation and functionalization. Although, in general, this type of carbonyl methylenation can be performed with the Wittig reaction or with the Peterson alkenation, in many cases these methods are not suitable or proceed in low yields. For example, readily enolizable aldehydes and ketones are generally not good substrates for Wittig-type methylenations, due to the basic nature of the reagents that convert the carbonyl groups into the corresponding enolates. Also, the methylenation of esters, lactones, amides, and other types of heteroatom-substituted carbonyl compounds often does not proceed under Wittig or Peterson reaction conditions due to the competing cleavage of the carbonyl-heteroatom bond and the formation of alternative products. Thus, despite the great utility of the Wittig and Peterson alkenation reactions, there are many types of carbonyl derivatives that cannot be employed as substrates in these processes.

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Meeeee 8 Meeeeeeeeeeee eeee Meeeeeeee Meeee Meeeeee ee Meeeeee[‌88‌,‌88‌]

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Meeeeeeeeeee Meeeeeeee

(μ-Meeeee)eee(η8-eeeeeeeeeeeeeeee)(eeeeeeeeeeeeeeee)(μ-eeeeeeeee)eeeeeeee (88, Meeee Meeeeee):[‌88‌,‌88‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

Meee Me8Me (88eM, 888eeee) eee eeeee eee eeeeeee ee e eeeeeeeeee ee Me(Me)8Me8 (88; 88e, 888eeee) ee eeeeeee (888eM) eeeee e eee M8 eeeeeeeeee eeee eeeeeeeee ee eeeeeeee, ee eeee e eeeeeeeeeee eee eeee. Meeeeeeee ee MM8 eeeee eeeeeeeeeee. Meeee eeee, eee eeee eee eeeeeee eee 88e, eee eee eeeeeeeee eeee eeeeeee ee eeeeee eeeeeeeeeeee eeee e eeee eeee (MMMMMMM: eee Me8MeMe eeeeeee eeeeee eeeeeeeee eeee eeeeee eeeee eee eee eeeeeeeeeee eeeeee ee eeeeeeeee). Mee eee eeeeeeeeeee eee eeeeeeeeeee ee eeeeeee (888eM), eee eee eeeeeeeee eeee eee eeeeeee eeee Me8Me (88eM, 888eeee) ee eeeeeee (888eM). Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee e eee ee Meeeee eeeeeeeee ee e eeeeee eeee, eee eeee eeeeeeeeeeee ee eee eeeee ee eeeeeeeeee (~888eM eeeee eeeeee). Meee eeeeeeeee eeee eee eeeeeeeee eeeeeee eeee ee eeeee eeeeee ee eeeeee eee eeeeeee ee eeeee eeeeeeeeeee ee 88°M eee 88e. Mee eeeeeeeeeee eee eeeeeee eee e eeeeeee, eee eee eee eeeeeeeeeee eeee eee eeeeee eeee eeeeeeeee eeeee ee 88°M. Mee eeeeee eeee eeeee eeeee eeee eeeeee ee eeeeee eeeeeee eeeeee eeeeeeee; eeeee: 8888e (8888%).

Meeeeee Meeeeeee ee (μ-Meeeee)eee(η8-eeeeeeeeeeeeeeee)(eeeeeeeeeeeeeeee)(μ-eeeeeeeee)eeeeeeee (88, Meeee Meeeeee):[‌88‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

M eeee ee Me(Me)8Me8 (88; 8.88e, 88.8eeee) eee 8M Me8Me ee eeeeeee (88eM, 88eeee) eee eeeeeeee eeeee eeeee. Meeee 88e, eee eeeeeeeee eeee eeeeeee eeeee eeee eeeeee, eee eee eeeeeee eee eeeeeeeee ee eeeee, eeeeeeeeeeee eeeeeee (88eM). Mee eeeeeeee ee eee Meeee eeeeeee eee eeeeeeeeee ee eeeeeeeee 8eM ee eee eeeee eeee eeee MeMMe (8.88eM, 8.88eeee) eee eeeeeeee (8 eeeee) ee ee MMM eeee eeeee eeeee. Meeee 88e, eee eeeee ee eeeeee eeeeeeee ee eee 8M MMM eeeeeeee ee eeee eeeeeee eeeeeeeee 88% eeeeeeeeee eeee eeeeeee. Meeeeeeeeee, eee eeeeeeeeeeeee ee eee eeeeeee eee eeeeeeeeeeeee 8.88M. Meee eeeeeee eeee ee eee Meeee eeeeeee eee eeeeeee ee 8.8M eeeee eeeee, eee eeee eeeeeeee ee eeeeeee eeeeeeeee.

8,8-Meeeeeee-8-eeeeeeeee-8-eee (88, M8=Me; M8=e-Me); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eee eeeeeeee eeeeeeee 88 (M8=Me; M8=e-Me; 8eeee) ee MMM (8eM) eeeeee ee 8°M eee eeeee e 8.8M eeee ee eee Meeee eeeeeee 88 ee eeeeeee (8eM, 8eeee). Meeee eee eeeeeee eee eeee eeeeeee eee 88eee, Me8M (~88eM) eee eeeee, eeeeeeee ee eee eeee eeeeeeee ee 8.8M ee MeMM (88 eeeee) ee eeeeeee eee eeeeee Me eeeeeeeee. Mee eeee eee eeeeeee eee eeeee (Me8MM8), eeeeeeee eeeeeee Meeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeee eeeeeee, eeeeeee/Me8M 88:8 ee 88:8); eeeee: 88%.

(8-Meeeeeeeeeeeeeeeeee)eeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

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References