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1.1.7.2 (Halomethyl)zinc-Mediated Cyclopropanation Reactions

DOI: 10.1055/sos-SD-212-00164

Belderrain, T. R.; Nicasio, M. C.Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (20141269.

The reaction of an alkene with diiodomethane in the presence of activated zinc generates a cyclopropane derivative in high yield. This process, known as the Simmons–Smith cyclopropanation,[‌66‌,‌67‌] is one of the most important methods for the synthesis of cyclopropanes (Scheme 12);[‌1‌,‌12‌,‌15‌,‌69‌] see also Science of Synthesis, Vol. 48 [Alkanes (Section 48.2.1.4.3)]. The reaction is stereospecific with respect to the geometry of the alkene and proceeds through a butterfly-type transition state involving a zinc carbenoid from which the methylene group is transferred to the alkene.[‌70‌,‌71‌]

Meeeee 88 Meeeeee–Meeee Meeeeeeeeeeeeeee Meeeeeee[‌8‌,‌88‌,‌88‌,‌88‌]

Mee eeeeeeeeeeeeeee ee eeeeeee eeeeeeee ee eee eeeeeeee Meeeeee–Meeee eeeeeeee eeeeeee eeee eee eeeeeeeeeee ee eee eeee/eeeeee eeeeee.[‌88‌] Meeeeeeee, eeeeeee eeeeeeeeeeeee eeee eeee eeeeeee eee eee eeeeeeeeee ee eee eeee eeeee eeeeeeeee eeeeeeeeee,[‌88‌] eeeeeeeeeee ee eeee ee eeeeeeeee eeee eeeeeee,[‌88‌] eeeeeeeeeee ee eee eeee/eeeeee eeeeee eeee e eeee/eeeeee eeeeee,[‌88‌] ee eee eeeeeeee ee e eeeeeeeee eeeeee ee eeeeeeeeeeeeeeeeeeeee ee eeeeeee eee eeeeeeee.[‌88‌] Meeeeeeeeeee, eeeeeeeeeeee ee eee eeeeee ee eee eeee eeeeeeeee eeeeeeee eeee eeee eeee eeeeeeeee (Meeee 8). Meeee eeeeeee eee eeeeeeeeeee ee eee(eeeeeeeeeeee)eeee (Meeeee),[‌88‌] eeeee(eeeeeeeeee)eeee (Meeeeeee),[‌88‌] (eeeeeeeeeeee)(eeeee)eeee (Meeeeee),[‌88‌] (eeeeeeeeee)(eeeeeeeeeeeeeeee)eeee (Mee),[‌88‌] eee (eeeeeeeeee)(8,8,8-eeeeeeeeeeeeeeee)eeee (Meeeeeee).[‌88‌] Meeee eeeee eeeeeeeeee eeee ee eeeee ee eeeeeeee[‌88‌] eee eeeeeeee[‌88‌] eeee eeee eeeee ee eeeeeee eeee eeee eeeeee ee eeeeeeeeeeeeeeee eeeeeeee. Me eeeeee ee eeeee, eeeeeee, eeee eeee eeee-eeeeeeee eeeeeeeeeeeeeeee eeeeeeeee eee eeeeeee eee eeeee eee eeeeeeeee Meeeeee–Meeee eeeeeee (Me/eeeeeeeee eee MM8M8). Meeeeeeeeeee, eeee eeeeeeeeeeeeeeee eeeeeee eee eeee ee eeeeeeeeee eee Meeeeeee eeeeeeeeeeee ee eee eeeeee ee eeeeee, eeeee ee eeeeee eee eeeeeeeeeeeeeeee eeeeeeee ee ee eeeeeee eee ee eeeeeeeeeeeeeee eeeeeeee (e.e., MM8Me8), eeeee eeeeeeee eee eeeeeeeeee ee eee eeee eeeeeeeeee. Mee eeeeeee (eeeeeeeeee)(eeeeeeeeeeeeeeee)eeee eee eeeeee ee ee eeeeee eeeeeeee eee eeeeeeeee ee eee eeeeeeeeee eeeeeeeeeeeeeeee ee eeeeeeeeeeeeee eee eeeeeeeeeeeeeeee eeeeee eeeeeee.[‌88‌]

Meeee 8 Meee Meeeeeee eee Meeeeeeeeeeeeeee Meeeeeeee[‌88‌,‌88‌‌88‌]

Meeeeee Meeeeeeee Mee
MMe(MM8M) Me/eeeeeeeee, MM8M8 [‌88‌,‌88‌‌88‌]
Me(MM8M)8 MeM8, MM8M8 [‌88‌]
MeMe(MM8M) Me8Me, MM8MM (M = M, Me) [‌88‌,‌88‌]
M8MMM8Me(MM8M) MMM, Me8Me, MM8M8 [‌88‌]
8,8,8-Me8M8M8MMe(MM8M) 8,8,8-Me8M8M8MM, Me8Me, MM8M8 [‌88‌]

Mee Meeeeee–Meeee eeeeeeee eee ee eeeeeee ee eeeeeeeeeeeeee eeee eeeeee eee eeeeeee eeeeeee eee eee eeeeee eeeeeeeee eee eeeeeeee ee eeeeeee eeeeeeeeee eeeeee ee eee eeeeeee, eeee ee eeeeee, eeeeee, eeeeeee, eeeeeeee, ee eeeee, eeeee eeeeee. Me eeeeeeeeee, eee eeeeeeee ee e eeeeeee ee eeeee eeeee ee eee eeeeeee eeeeeeee eeeeeeee eee eeeeeeee eeee[‌88‌] eee eeee eeeeeeeeee-eeeeeeeee eeeeeeee eee eeee eeeeeeeeeeee eeeeeeeee ee eeeeeee eee eeeeeeeeeeeeeeeee ee eee eeeeeeee, ee eee eeeeeee ee eee eeeeeeeeee eeeeeeeeeeeeeeee ee e eeeeee eeeeeee eeeeeee eeeeeee ee eeee eeeeeeeeeee eeeeeeee 88 (Meeeee 88).[‌88‌] Meeeeee e eeeeeeeee eeeee, eee Meeeeee–Meeee eeeeeeeeeeeeeeee ee eeeeee ee eeeeee eeeeeee, ee ee eee eeeeeeeeeee ee eeeeeeeeeeee 88.[‌88‌] M eeeee eeee ee eeeeeeeeeee eee eeee eeeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeeeeeeee eeee eeeeeeeeeeee eeeeeeeeeee,[‌88‌,‌88‌] ee eeeee ee eee eeeeeeeeee: eee eee ee eeeeee eeeeeeeeeee eee eee eee ee eeeeee eeeeeee (Meeeee 88). Mee eeeeeeeeeeee-eeeeeee eeeeee eeeeeeeee ee 88[‌88‌] eee eeeeeeeeeeeeee eeeeee eeeeeee eee eeeeeeeeeeeeeeeeeeeeee eeeee, e.e. 88,[‌88‌] eeee eeee eeee ee eeeeeee eeeeeeeeee eeeeeeeeeeeeeeee. Me eee eeeee eeee, eeee eeeeeeeeeeeeee eeeeee eeeeeee eee eeee eeeeeeeeee eee eeeeeeeeee eeeeeeeee, eee eeee e eee ee eeee eee ee eeee ee eeeeeeeee eeeeeeeeee eeee ee eee MMMMM-eeeeeee eeeeeeeeee eeee 88[‌88‌,‌88‌] eee eeeeee eeeeeeeee 88.[‌88‌]

Meeeee 88 Meeeeeeeeeeee ee Meeeeee–Meeee Meeeeeeeeeeeeeee eeee Meee Meeeeeeeee[‌88‌,‌88‌]

Meeeee 88 Meeeeeeeee Meeeeee–Meeee Meeeeeeeeeeeeeeee[‌88‌,‌88‌,‌88‌‌88‌]

Meeeeeeeeeee Meeeeeeee

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

MMMMMMM: Meeeeeeeeee ee e eeeeeeeeee eee eeeeeeee eeeeee.

Me e eeee ee (M)-8-eeeeeeeee-8-ee-8-ee (888 ee, 8.8 eeee) ee eeeee MM8Me8 ee −88 °M eee eeeee eeeeeeee Me8Me (8.8 eM, 88 eeee) eeeeeeee ee MM8M8 (888 µM, 88 eeee). Mee eeee eee eeeeeee ee eeee ee ee eeee 8 e eee eee eeeeeee eee eeeeeee eee ee eeeeeeeeee 8 e, eeeee eeeee eeee MMM eeeeeeee eeeeee eeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee. Mee. ee MM8Me (88 eM) eee eeeee eee eee eeeeeee eee eeeeeee eeee Me8M (88 eM) eee 88% ee MMe (88 eM). Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeee eeeeeeeeeeee eeeeee eeee eee. ee Me8MM8 (88 eM), eee. ee MeMMM8 (88 eM), eee eee. ee MeMe (88 eM). Mee eeeeeee eeeee eee eeeee (MeMM8) eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeee eeeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 88:88) ee eeee eee eeee-eeeeee; eeeee: 88 ee (88%); eee eee eee-eeeeee; eeeee: 888 ee (88%).

(8M,8M)-{8-Meeee-8-[(eeeeeeeeeeeeeeeeee)eeeeee]eeeeeeeeeee}eeeeee 8,8,8-Mee-M-eeeeee-β-e-eeeeeeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeeee ee e eeeeeeeeee eee eeeeeeee eeeeee.

Me e eeee ee eeeeeeeeeeeeeee 88 (8.88 e, 88.8 eeee) ee MM8Me8 (888 eM) eeeeee ee −88 °M eee eeeee ee eee eeeeeee Me8Me (8.8 eM, 88.8 eeee). Meeee 88 eee ee eeeeeeee, MM8M8 (8.8 eM, 88.8 eeee) eee eeeee ee eee eeee eeee 8 eee. Meee MMM eeeeeeee (MeMMe/eeeeee 88:88) ee eeeeee eeeeee eee eeeeeeeee (88 e), eee eeeeee eeee eee eeeeee eeeeee eeee e eeeeeeee eeeeeee ee Me8M (888 eM) eee eee. ee MM8Me (88 eM) ee 8 °M. Me eeee eeee eee eeeee e eeeeeee eeeeee ee 88% ee MMe ee eeeeeeee eee eeeee eeeeeeeeeee. Mee eeeeee eeee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee 8.88 M ee Me8MM8 (88 eM), eee. ee MeMMM8 (88 eM), eee eee. ee MeMe (88 eM). Mee eeeeeee eeeee eee eeeee (MeMM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee ee eee eeeeeeee eee eeeeeeee ee MMMM [8 ee eeeeee eee MMMM-MMM, 8 ee × 88 ee; MeMMe/eeeeee 8:88; eeee eeee 8 eM · eee−8; eM (eeeee) 88.8 eee; eM (eeeee) 88.8 eee] ee eeeeeeeee e ee ee >888: 8. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (MeMMe/eeeeee 8:88) ee eeee e eeeeeee, eeeeeeeee eee; eeeee: 8.8 e (88%). Meeee eeeeeeeeeeeeee, MMMM eee 8M MMM eeeeeeee eeeeeeeee eee eeeeeeee ee eeee eee eeeeeeeeeeee; Me 8.8 (MeMMe/eeeeee 8:8); [α]M −88.8 (e 8.8, MMMe8).

(8M,8M)-(8-Meeeeeeeeeeeeeeee)eeeeeeee (88); Meeeeee Meeeeeeee Meeee Meeeeeeeee Meee 88:[‌88‌]

MMMMMMM: Meeeeeeeeee ee e eeeeeeeeee eee eeeeeeee eeeeee.

Me e eeee ee eeeeee eeeeeeeeee eeee 88 (88 ee, 8.8 eeee, 8.8 eeeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) ee −88 °M eee eeeee Me8Me (88 µM, 8.8 eeee, 8.8 eeeee) eeeeeeee. Meee eeee eee eeeeeee eee 88 eee eee eeee MM8M8 (8 µM, 8.8 eeee, 8.8 eeeee) eee eeeee eeeeeeee. Mee eeee eee eeeeeee eee ee eeeeeeeeee 88 eee eee eeee e eeee ee 8-eeeeeeeeee-8-eeee eeeeeeeeeeeee eeeee (888 ee, 8.8 eeee, 8.8 eeeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) eee eeeee eeeeeeee. Mee eeeeeee eee eeeeeee eee 8 e. Me e eeeeee eeeee eeeeeeeeee Me8Me (88 µM, 8.88 eeee, 8.88 eeeee) eee MMM (88 µM, 8.88 eeee, 8.88 eeeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) ee −88 °M eee eeeee MM8M8 (88 µM, 8.8 eeee, 8.8 eeeee) eeeeeeee. M eeeee eeeee eeeeeeeeee eee eeeeee eee, eeeee 88 eee ee eeeeeeee, eeee eeeeeee eee eeeee ee eee eeeeeeee ee eee eeeee eeeee. Mee eeeeeeeee eeee eee eeeeeee eee 8.8 e. Me e eeeee eeeee eeeeeeeeee Me8Me (88 µM, 8.88 eeee, 8.88 eeeee) eee MMM (88 µM, 8.88 eeee, 8.88 eeeee) ee 8,8-eeeeeeeeeeeeee (8.8 eM) ee −88 °M eee eeeee MM8M8 (88 µM, 8.8 eeee, 8.8 eeeee) eeeeeeee. Mee eeeeeee eee eeeeeee eee 88 eee, eeeee eeeee e eeeee eeeee eeeeeeeeee eee eeeeeeee. Meee eeeeeee eee eeeee ee eee eeeeeeee ee eee eeeee eeeee eee eee eeeeeeeee eeee eee eeeeeee eee 8.8 e. Mee eeeeeeee eee eeeeeeee eeee 8.8 M ee M8MM8, eeeeee eeee 8.8 M ee M8MM8 (88 eM), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeee eeee eeeeeee eee eeeeeeeee ee MMM (88 eM), eee 8.8 M ee M8MM8 (88 eM) eee MM8M (888 ee, 8 eeee, 8 eeeee) eeee eeeee. Mee eeeeeeeeeeeee eeeeeee eee eeeeeee eeeeeeeeee ee 88 °M eee 8.8 e. Mee eeeeeee eee eeeeeeeee eeee MM8Me8 (88 eM), eeeeee eeee eee. ee MeMe (88 eM), eee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (Me8M/eeeeee 8:8) ee eeeeee e eeeeee eee; eeeee: 888 ee (88%); Me 8.88 (MeMMe/eeeeee 8:8); [α]M88 −88.8 (e 8.88, MMMe8).

References