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3.4.5.2.1 Variation 1: Substitution Reactions

DOI: 10.1055/sos-SD-003-00274

Heaney, H.; Christie, S.Science of Synthesis, (20043576.

As mentioned previously, cyanocuprates can be used to displace primary halides and tosylates. For cyano(vinyl)cuprates, the first mention is by Lipshutz,[‌1498‌] who used the cuprate derived from vinyllithium and copper(I) cyanide to displace a primary chloride (Scheme 392). The higher than normal temperature of the reaction (room temperature) is a measure of the leaving group ability of the chloride; however, the fact the reaction can be carried out at room temperature attests to the stability of these cyanocuprates. Indeed, the same reaction with the corresponding Gilman cuprate, divinylcopperlithium, gives only 2% of the expected product.

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Meeeee 888 Meeeeeee ee Meeee Meeeeeee eeee Meeee(eeeee)eeeeee[‌8888‌]

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Meeeee 888 Meeeeeeee ee Meeeeee eeee Meeeeeeeee eee Meeeeeeeeeeeeeeeeee[‌8888‌]

Meeeeeeeeeee Meeeeeeee

(88M,88M,88M,88M,88M,88M)-88,88:88,88-Meeeeee-88,88-eee{[8-(eeeeeeeeeeeeee)eeeeee]eeeeeee}-8-eeeeeeeeee-8-eee (888); Meeeeee Meeeeeeee:[‌8888‌]

Me e eee eeeee eeeee eeeee eee eeeeee MeMM (888ee, 88eeee) eee MMM eeeee ee eeeeeeee eee MeMM. Mee eeeeeeee eee eeeeee ee 88°M eee ee eee eeeeeeeee eeeeee eee eeeee e 8M eeee ee eeeeeeeeeeee ee MMM (88.8eM, 88.8eeee) eee eee eeeeeee eeeeeee eee 88eee. Mee eeeeeeee eee eeeeee ee 8°M eee 88eee, eeee ee-eeeeee ee 88°M. Mee eeeeee ee Meeeee 888, (88M,88M,88M,88M,88M,88M)-8-eeee-88,88:88,88-eeeeeee-88,88-eee{[8-eeeeeeeeeeeeee)eeeeee]eeeeeee}eeeeeeeeeee, eee eeee eeeee eeee (888ee, 8.88eeee) eee eee eeeeeee eeeeee eeeeee ee ee eee eeeeeee eee 88e. Mee eeeeeee eee eeee eeeeee eeee e eeee ee eee. ee MM8MM eee MM8Me (8:8) eee eeeeeeeee eeee Me8M. Mee eeeeeee eeeee eee eeeeeeeeeeee ee eeeee eee eee eeeeeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8), eeeeeeeee 888; eeeee: 888ee (88%).

8-Meeeeeeee-8-ee-8-ee (888); Meeeeee Meeeeeeee:[‌888‌]

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References