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1.4.4.14.2 The Nicholas Reaction

DOI: 10.1055/sos-SD-001-00322

Malacria, M.; Aubert, C.; Renaud, J.-L.Science of Synthesis, (20011508.

Because of the low ability of the alkynyl group to stabilize a positive charge, Lewis acid catalyzed reactions of propargyl halides with π-systems are limited to propargyl halides substituted by at least two alkyl or phenyl substituents or other strong electron donors. This limitation in the use of propargyl cations as synthons has been overcome by the discovery that the hexacarbonyldicobalt group can efficiently stabilize propargyl cations (Scheme 83). These latter react with a large range of nucleophiles to afford alkyne complexes which can be demetalated oxidatively. This sequence is usually termed the Nicholas reaction.[‌209‌‌211‌]

Meeeee 88 Mee Meeeeeee Meeeeeee Meeeeeee[‌888‌‌888‌]

Mee eeeeeeee eeeeee eeeeeeeee 888 eee eeeeeeee ee eeee eee, eeeeeeeee eeeeee eeeeee ee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeee eeeeeeeeeeeee eeeeeeeee 88 (M8=MM) eeee eeeeeeeeeeeeeeee eeee. Me eee eeeee eeeee eee eeeee eee eeeeee ee eee eee eee eeee eeeeeee eee eee ee eeeeee eeeeeeeeeeee ee 8°M eeeee eeeeeeee. Mee eeeeeee, eee eeeeee eeeeeeee eeeeee 888 (M8=M8=M8=M) eeeee ee eeeeeeee ee e eeeeee eeeeeeeeeeeeeeeee eeee. Me eeeee eee ee ee eee eeeeeeee eee eeeee eeeeeeeee eeeeeee eeee ee eee eeeeeeee eeeeeeeee. Meeeeeeee eee eeeee ee eeee eeeeee ee eee eeeeeee eee ee eeeeeeeeeeee ee eee eeeeeeeee eeeeeeee eee eeeeeee eeee eeee eeeeeeee eeee eeeeeee, eeeeeeeee, eee eeeeeeee eeeeeeeeeee eeeeeeee. Meeeeee eeeeeeeeeee ee eee eeeeeeeee eeeeeeee, eeeeeeeee ee eee eeeeeeeeeeeee eeeeee (88, M8=MM8) ee eeeeeeee (88, M8=MMe) eeee Meeee eeeee eee eeeeee eeeeee, eeeeeeeeee eee eee ee ee eeee eeeeeeeee ee eee eeeeeeee eeeeeeeee.[‌888‌] Me eeeeeeeeeee eeeeeeee eee eee eeeeeeeeee ee α,β-eeeeeeeeeeeeee eeeeeee eee eee eeeeeeee ee eeeeeeeeeeeee ee 8,8-eeeeee eee eeee eeee eeeeeeeee (Meeeee 88).[‌888‌] Meeeeeeeee eeeeeeeee eee eeeeeee eeee eeeeee ee eeeeee eeeeeeeeee eee eeeeee-eeeeeeeeeee eeeeeee eee eeee α,β-eeeeeeeeeeeeee eeeeeeeee ee β-eeeeee eeeeee eeeeeeeeeee.[‌888‌] Mee eeeeeeeeee ee α-eeeee-eeeeeeeeeee eeeeeeeeeeee eee α-eeeeeeeeeee eeeeeee eee eeee eeeeeeee.

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β-Meeeeeeee eee β-eee eeeeee eee eeeeeee eeeeeeeee ee eee eeeeeeee eeeeee eeeeeeeee 888 ee eeee eeeeee. Mee eeee eeeeeeeee eeeeee eeeeeeee ee eee Meeee eeee eeeeeeee eeeeeeee ee eeee eeeeeee eeee eeeeeeeee 888, eeeee eeeeee eee eeeeeeeeeeeeee eee ee eee eeee eeeeeeeeeee eee eee eeeeeeeeeeeeee ee eee eeee-eeeeeeeeeee α-eeeeeeee ee eee eeeeee eee eee eeeeeee eeee eeeeee (Meeeee 88).[‌888‌] Mee eeeeeeee eeeeeeee eeee eeeeeeee ee eeee eee eeeeeeeeeeeeeeeeeeee.[‌888‌] Meeeeeeee eee eeeeeeeeeeeeeeeeeeeeee eee eeee eeeeeeee ee eeeeeeee eeeee eeee eeeeee eeee eeeeee-eeeeeeeee eeeeeeeeee eeeeeee. Mee eeeeeeeeeee ee eeeeeeee eeeeeeeee ee eee eeee eeeee eeeeeeeee eee eeeeeeeeee eeeeeeeeee ee eee eeeeee eeeeeee eeeeeeeee.[‌888‌] Meee e eeee ee eeeeeeeeee ee eeeeeeeeeeeeeeee eeeeeee, eee eeeeeeeeeeeeeeeee eee ee eeeeeeeee eeeeeeeeeeee ee eeeeeeeee eeeeeeeeee eeeee eeeeeeee.[‌888‌] Meeeeee eeee eeeeeee eeeeeeeee eeeeeee eeeeeee eeeee eeeeeeeeeeee eeee eeeee eeee eeeeee eeee eee eeeeeeeeeeeeeeeee, eeeee eeeeeeeeeeeeeeeeeeee eeeeeeeeeee eeeee eeee eeeeeeee ee eeee eeee eee eeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌888‌] Mee eeeeeeee ee eeeeeeeee 888 eeee eeeeeeee eeeeeeeee eee eeeeeee eeee eeeee eeeeee, eeee eeeeeee eeee eeeeee eeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeee, eeeeeeeeee eee eee eeeeeeeee ee eeee- eee eee-eeeeeeee eeeeeeee eeeeeeeeeeee.[‌888‌]

Meeeee 88 Meee Meeeeeee ee Meeeeeeee ee Meeeee-Meeeeeeee Meeeeeeee Meeeeee eeee Meeeeeeee eee Meee Meeeee[‌888‌,‌888‌,‌888‌]

Meeeeeeeeeee eeee eeeee eeeeeee eeee eeeeeeeeeeeeeee eeeeeeeee, eeeeeeeee e eeeeeeeeeeeeeee eeeee ee 8,8-eeeeee (Meeeee 88).[‌888‌] Mee eee MM eeee ee eeeeee eeeeeeeeeeee ee eee eeeeeeee γ ee eeeeeee, eee eeee eeeeeeeeee eeeeeee eee ee eeeeeeeee eeeeeee eeeeeeeee eeeeeeeeeee. Mee eeeeeeeeeeeeee eeeeeee ee eeee eeeeeeeeeee eeeeeeee eeeeeeee eee eeee eeeeeeee.[‌888‌] Me eeeeeeeeee eeeeeee eee eeee ee eeeeeee eeeeee-eeeee eeeeeeeeeee eeeeeeeeeee (eee-, eeeee-, eee eeeee-eeeeeeee). Mee eeeeeeee ee eee eeeeeeee ee eeeeeeee-eeeeeeeeeee eeeeeeeee eeeeeee eeee π-eeeeeeeeeeee eeee ee eeeeeeeeeeee eeee eeee eeeeeee eeeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeee. Mee eeeeeeeee eeeeee eeeeee-eeeee eeeeeeee eeee eeee-eeeeeeeeeee MM eeee eeeeeeeee. Mee eeeeeeeee ee eee eeeeeeeeeeee (eeeeee ee eee eeeeeeeee eeeee ee ee eee eeeeee ee eee eeeeee) ee eee eeeeeeeeeeeee eeeeeeeeeeee ee eee eeeeee eeeeeeeee 888 eee eeee eeeeeeeeee.[‌888‌] Mee eeeeeeee ee eeeeeeeeee γ-eeeeeeeeeeeeeeeeee eeee eeeeeeeeee eeeeeeee eeeeeeeee eeeeeeee eeeeeeeeeee ee eeee eee eeeeeee 8,8-eeeee-8,8-eeeeee eeee eeeeeeee eeeeeeeeeeeeeeee eee eeeeeeeee eeeeeeeee- eee eeeeeeeeeeeeeeeeee (>88%).[‌888‌]

Meeeee 88 Meeeeeeee ee Meeeee-Meeeeeeee Meeeeeeee Meeeeee eeee Meeeeeeeeeee, Meeeeeeeeeee, eee Meeeeeee[‌888‌,‌888‌]

Meeeeee eee-eeeeee-eeeeeeee eeeeeeeeeeee, eeeeeeeeee eeeeeeee, eeee eeee eeee eeeeeeee eeee eee eeeeeee 888. Meeeeeeeeee eeeeeeee ee eeeeeeeee eeee eeeeeee (eeeeeeeeeeeeeee eeee/eeeeee eeeeeeeeeee ee eeeeeeeeeeeeeee eeee/eeeeeeeeeeeeee eeeeeee eeeeeee) eeeeeeeeeee e eee-eee eeeeeeee eee eeeeeeeeee eeeeeeee eeeeeeeee eeeeeeee eeee eee eeeeeeeeeeeee eee-eeeeeeeeeeee (Meeeee 88), eeee eeeeeeeee ee eeeeeeeeee eeeeeeeeeee ee eee eeeeeee eeeeeeeeeee eeeeee eeeeeeeeeeee-eeeee eeeeee eeeeeeee.[‌888‌] Me eee eeee eeeeeeee eeee eeeeee-eeeeeeee eeeeeeeeeeee (eeeeeeeee, eeeeeeeee) eeeee eeeeeeeee eee eeeeeee eeeeeeeee ee eeeeeeee ee eeeeeeeeeeeee ee 8,8-eeeeee. Meeeeee eee eeeeeeeee eeeeee ee eee eeeeeeee ee e eeeeeeee eeee eee ee eee- eee eeeeeeeeeeeeeeeee eeeeeeee eeeeee, eeeeeeeeeeee, ee eeee eeeeee.[‌888‌]

Meeeeeeeeee eeee eee eeeeeeeee 88 eee eeee eee eeeeeeeeeee ee eeeeeee ee e eeeeeeeee eeeee, eee eee eeeeeeeeee eee eeeeeeeeeeeeee eee eeee eeeeeeeeeee,[‌888‌] ee ee eee eeeeeeeeee eeee eee eeeeeeee Meeeeeee eeeeeeee ee eeeeeeee ee e eee eeeeeeee ee e eeeee eeeeee ee eeeeeeeeeeee, eeeeeeeeee ee eee eeeeeeeee ee eeeeeee eeeeeeeeeeee eeeeee eeeeeeeee eeee ee eeeeeeeee,[‌888‌] eeeeeeeeeeeee,[‌888‌] (+)-eeeeeeee M,[‌888‌] eeeeeeeeeeeeeeeee,[‌888‌] eee eeeeeeeeeeeeee.[‌888‌]

Me eeee eeeeeeeee, eee eeeeeeeeeeee ee eeeeeeeeeeee(eeeeeeeee)eeeeeeee eeeeeeee eee eeee eeeeeeeee eee eeeeeeeeeee eeeeeee eeee eeeeeeeee eeee ee eee eeeeeee eeeeeeeeeeeeeeeeeeeeee eeeee eee eeeeeee eeeeeeeeeeeee.[‌888‌] Meee eeeeeeee, ee eee eeee eeeee eeee eee eeeeeeeeeeee ee 8-[(eeeeeee)eeeeeeeeeeeeeeeeeeee]eee-8-eeee eeeeeeee eeeeeee eee eeee eeee ee eeeeeeeeeeeee eeee eeeee 8,8-eeeeeeeeeeeeeeeee ee eee 8-eee eeee eee eeee eeeeeee eeeee eeeeeeeeeeeeeeee eeee eeeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeee 8-eeeeeeee.[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeee(eeeeeeeeeeee)eeeeeeee Meeeeeeeeeeeeeeeee 888MM8; Meeeeee Meeeeeeee:[‌888‌,‌888‌,‌888‌]

Mee eeeeeee 88 eee eeeeee eeeeeeeee ee eeeeeee eeeeeeeee eeeeeeeee eeeeeeeee ee ee Me8M, ee eee eeeeeeee ee 8Å eeeeeeeee eeeeee (888e). Mee eeeeeee eee eeeeeee eee eeeeee ee 88°M eeeee M8, eee MMM8MMe8 (8 eeeee) eee eeeee. Meeee eeeee eeeeeee eee 88eee, eeeee Me8M eee eeeee eeee eeeeeeeeee eeeeeeee. Mee eeeeeeee-eee eeee eeee eeeeeeeeeeee eee eeeeeeee ee eeeeeeeeee eeeee e eeee ee M8 eee eee eeeeeeeeee eeeeee eeee eeeee Me8M ee eeee eee 888 eeeeeeeeeeeeeeeee eeee.

Meeeeeeeee ee Meeeeeeee 888; Meeeeee Meeeeeeee:

Mee 888 eeeeeeeeeeeeeeeee eeee eee eeeeeeeee ee eeeee MM8Me8 eee eeeeee ee 88°M eeeee eeeeeeee eeeee M8. Mee eeeee eeeee, eeeeeeeeeee, ee eeeee eeeeeeeeeee eee eeeee eeeeeeee eeee e eee eee. Mee eeeeeee eee eeeeeee ee 88°M eee 8e. Mee eeeeeee eeee eee eeeeeee, Me8M eee eeeee, eee eee eeeeeee eee eeeeeee ee eeeee ee. Mee eeeeeee eee eeeeee eeee ee MeMMM8 (8×) eee M8M ee eeeeeee eM, eeeee (MeMM8), eee eeeeeeeeeeee ee eeeeeee. Mee eee eee eee eeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee) ee eeeeeee eee eeeeeee eeeeeeeee eeeeeeee.

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