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Please login or sign up for a free trial to access the full content. 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.

Meeeee 888 Meeeeeeeeeee ee e Meeeeee Meeeeee Meeee eeee Meeeeeeeeeeeeeeeeee[‌8888‌]

Meee eeeeeeeee eee eeee eeeeeee ee eeeeeee eeeeeee eeeeeeeee.[‌8888‌] Meeeee eee eeeeeeeee ee (+)-eeeeeeee, ee Meeeeeeeeee eeeeeeeeee, e eeeeeeeeeeeeeeeeeee ee eeee ee eeeeeeee e eeeeeeee eeeeee ee eeeeeeeee eeeee, eeeeee 888 (Meeeee 888).

Meeeee 888 Meee ee eee Meeeeeeee ee (+)-Meeeeeee eee Mee ee Meeeeeeeeeeeeeeeeee[‌8888‌]

Meeeeeeeeeee ee ee eeeeee ee ee eeeeeeeee eeee eeeeeeeeee eeeeeeeeeee eee eeeeeee eee eeeeeeeeeee ee eeeeee eee eeeeeee eeeeeeeeeeee. Mee eeeeeeee eeeeeeee ee eeeeeeee eeeee eeee e eeeeeee ee eeeeeeeeeeeeeeeeeeee.[‌8888‌] Meeeeee eeeeeeeeee ee eeeee ee eeeeeeee eeee eeeeeeeee eeeee eeeeeee. Me eeeeeeee ee eee eeeee(eeeeee)eeeeeee eeeeeeeee eeeee, eee eeeee(eeeee)eeeeeee ee eeeeeeeeee ee eeeeeeeeee e eeeeeeeee eeeee eeeeee;[‌888‌] eeeeeee, eeeeee ee eeeeeee ee eee eeeeeee eeeee eeee eeee eeeeee eee eeeee.

Mee ee eeeee(eeeee)eeeeeeee ee eeee eeeeeeee (eeeeeeee) ee eeeeeeeeeeeeeee eee, ee eeeeeee, eeeeeeee ee eee eeeee eeeeeeee eee ee eee eeeeee eeeeeee. Me eee eeee eeeee, eeeeeee, eeee eeeeeeee eeee eeeeeeeeeeeee eeeee eeee ee e eeeeeee ee eeeeeee, eeeeeeeee 888 (Meeeee 888).[‌888‌]

Meeeee 888 Meeeeeee ee Meeeeeeeeeeee eeee Meeeeeeeeeeeeeeeeee[‌888‌]

Meee eeeeeeeee eee eeee eeee ee eee eeeeeeeee ee eeeeeeeeee eee eeeeeee eeeeeeeee eeeeeeeee eeeeeeeeeee.[‌8888‌] Meeee eee eeeeee eeeeeee ee Meeeee 888, eeeeeeee eeee eee eeeeeeeeeeeeeeeeeee eeeeeeee eeee eeee eeeeeeeeeeeee eeeeeee. Meeee eee ee eeee eeeeeeeeee eeeee eeeeeeeeeeeee eeeeeeee, eeeeeee. Meeeeeeeee ee eee eeeeeee eeee eeeeee eeeeeeee eeeeeeeeeeeeeee eeeeee. Meeee eeeeeeeeee eeeeeeee eeee eeeeeeee ee eee eeeee eeeeee, eee eeee eee eeeee eeee eeee eeeeeeeeeee, ee eeeeeeee eeee eeeee. Meee eeeeeeee eeeee eeeeeeeeee eee eeeeeeeeee ee eeeeeeeeeeeee eeee Meeeee eeeeeeee ee eeeeeee eeeee. Me eeee eeeeeeee, eee ee eee Meeeee eeeeeeeeeeee eeeeeeee eeee eeeeee(M) eeeeeee eeee eeee ee eee eeeeeeeeeee.

Meeeee 888 Meeeeeeeeeeee Meeeeee ee Meeeeee Meeeeeeeeeeee Meeeeeee eeee Meeeeeeeeeeeeeeeeee[‌8888‌]

Meeeeeee eeee eeeee eeeeeeee eeeee eee eeeeeeeee eeeeeee ee eeeeeeeeeeeee ee eeee eeeeeeeeeeee. Mee eeeeee eeeeeeee eeeeeee ee MM8 eeeeeeee, eeeee eeee e eeeee(eeeee)eeeeeee eeeeeeee e eeeeee. Meeee eee eeeee(eeeee)eeeeee eeeeeee, eeeeeee eeee eeeeeeee ee 8 eeeeeeeeee ee eeeeeeeeeeee ee eeeeee(M) eeeeeee, (e eeeee eeeee eeeeeee), eee eeeeeee eee eeeee ee eeeeee ee eee eeeeeeeeeeee eeeeeee ee eee eeeeeee (Meeeee 888).[‌8888‌] Meeee eee eeeeeee eeeeeee eeee eeeeee(M) eeeeee eeeee eeee eee MM8 eeeeeee.[‌8888‌]

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

Mee eee ee eeeeeeeeeeeee eee eee eeeeeeeeee ee eeeeeee eeeeeeeeeee eee ee eee eee eeeeeeee ee eeeeee eeeeeeee eeee Meeeeeee- eee eeeeeee-eeeee eeeeeee. Meeeeeee ee e eeeeeeeeeeee eeee e eeeeeeeee eeeee eeee ee eee eeeeeeeeeeeee eeeeee, eeee eeee ee eee eeeeeeee eeeee. Meeee eeeeeeeeeeeeeeeeeee, eeeeeee, eeeeeeee e eeeeeee, eee eeee ee eeeeeeeeeee (Meeeee 888). Mee eeeeeee eeeeeee ee eee eeeeeeee eeeee ee ee α,β-eeeeeeeeeee eeeeee. Meee ee, ee eeeeee, eeeeee ee eeeeeee Meeeeee eeeeeeee ee eee eeeeeeeeeeee ee eee eeeeeeee eeeeeee. Meeeeeeee eeee eeeeeeeeee e eeeeeeeeee eeeee ee eeeeeeeeeee eeeeeee ee eee eeee eeee eeeeeeeeee.[‌8888‌]

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]

Me e eee eeeee eeeee eeeee eee eeeee MeMM (888ee, 8.8eeee) eee MMM (8eM). Mee eeeeeeee eee eeeeee ee 88°M eee eeeeeeeeeeee (8.8eM, 8.8eeee) eee eeeee eeeeeeee; eee eeeeeeee eeeeeee ee eeee ee 8°M, eeee ee-eeeeee ee 88°M. Meeeeee eeeee (888μM, 8eeee) eee eeeee eee eee eeeeeeee eeeeeee ee eeee ee 88°M eee 8.8e, eeee 88°M eee 8e, eeee 88°M eee 8.8e. Mee eeeeeeee eee eeeeeeee eeee e eeeeeee ee ee MM8MM eee MM8Me, eeee eeeeeeeee eeee Me8M. Meeeeeeeeeeee ee eee eeeeeee eeeee ee eeeee eee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeeee 8:8) ee eee eeeee eeeeeee eeeeeeee 888; eeeee: 88ee (88%); eee 8-eeeeeeeee-8-ee-8-ee; eeeee: 88ee (88%), eeee ee eeeee eeee. Meeeeeee eeee eee 888: 8MMMM (MMMe8, δ): 8.88 (e, 8M, M=8Me), 8.8 (e, 8M, M=8Me), 8.88 (e, 8M), 8.8 (e, 8M), 8.8 (e, 8M).