Science of Synthesis

Malacria, M.; Aubert, C.; Renaud, J.-L., Science of Synthesis, (2001) 1, 512.

The Pauson–Khand reaction generates a cyclopentenone in a single step from an alkyne via its hexacarbonyldicobalt complex, an alkene, and carbon monoxide, with the last present as a ligand in the complex or added as the gas (‌Scheme 87‌). The overall process of this reaction is a formal [2+2+1] cycloaddition. The reaction was discovered in 1973 during a study of the reaction of various (alkyne)hexacarbonyldicobalt complexes with norbornadiene.[‌208‌] Since then, this reaction has attracted considerable interest among synthetic and organometallic chemists, as evidenced by the number of publications in the last two decades. Excellent reviews have been published and have compiled all the aspects of this reaction in terms of scope and limitations, mechanism, regio- and stereoselectivities, examples in inter- and intramolecular versions, and several synthetic applications.[‌339‌–‌343‌,‌400‌–‌402‌]

‌Meeeee 88‌ Meeeeee Meeeee eee eee Meeeee–Meeee Meeeeeee

Mee eeeeeeeee ee eee eeeeeeee ee eee eee eeeee eeeeeeeeeee; eeeeeee, eee eeeeeeeeeee eeeeeeeeeeee ee eee (eeeeee)eeeeeeeeeeeeeeeeeeee eeeeeee, ee eee eeeee eeeee ee eee eeeeeee, eee eeee eeeeeeeeeeee. Meeee eeeeeeeeeeeee eeeee eeeeeeeeee eeee eeeeee ee eeeeee eeeee eeee eeee eeee eeeeeeee.[‌888‌] Me ee eeeeeee eeeeeee eeee eeeeeeeeeeee ee eee eeeeee ee eee eeeeee eeee eeeee eeeee eee e eeeeeeeeeeee eeeeeeeee eeeeeeeee eeeeeee eeee ee eeeeee eeeeeeee, eeee eeeeeee eeeeeeeee eeeee eeeeeeeeee (‌Meeeee 88‌). Meeeeeeeeeee, eeeeeeeeeeee eeeeeeeee ee eee eeeeee π-eeee eeee eee ee eee eeeeee Me—M eeeee ee eee eeeeee eeeeeee eeeeee, ee eee eeee eeee ee eeeeeeee eeee eeee eee eeeeeee eeeeeeeeeee, eee ee eeeeeeee ee eeeeeeee ee eeeeee eeeeeeee ee eee eeeeeeeeeeeeee eeeeeeeeeee eeeeee eeee. Mee eeeeeeeeeee eeee eeeee eee eeeeeee ee eee eeeeeee ee e eeeeeeee eeeeeeee ee eeeeeeeee eeeeeeeee ee e eeeeee-eeeee eeeeee eeeeeeee eeeeeeee, eeeeeeee ee eeeeeee eeeeee eeeeeeee eeeeeeee, eee eeeeeee e eeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeeeeeee eeeeee. Mee eeeeeeeee eeeeeeee ee eee eeeeeeeeeeeeeeeeeeee eeeeeee ee eee eeeee eeeee eee eeee ee eee eeeeeeeeeeeeeeeeeeee eeeeee eeeeee eeeeee ee eeeee eeeeeeeeee ee ee eeeeeeeeee eeeeee eeeeeeeee eee eeeeeee.

‌Meeeee 88‌ Meeeeeeee ee eee Meeeee–Meeee Meeeeeee

Mee Meeeee–Meeee eeeeeeee eeeeeee eeeee eeee eeeee- eee eeeeeeeeeeeeeeeeeee. Meeee eeeeee eee eeeeeeeeeee eeeeeeeeee, eeeeee ee eeeeee eeeeeeeeeeee ee eee eeeeeeeeeeee eeeeee eeeeeeeee eeeeeee. Me eeeeeee, eee eeee-eeeeeeee eeee ee eee eeeeee eeeeeee eeee eee eeee-eeeeeeee eeeeee Me—M eeee ee eee eeeeeeee eeeeeee, eeee eee eeeeeeeeeee ee eeeeee eeeeeeeee eeeeeee eee eeeeee eeeeeee eeeeeeeeeee eeee eeee eeeeee.

Meeeee–Meeee eeeeeeeee eeee eeee eeeeeee eee eeeee eeeeeee eeeeeeee eeeeeeeee eeeee ee eeeeeeee eeeeeeeeee. Me eee eeee eeeeee eeee eeeeee eee eeeeeeeeeeeeee eeeeeeee, eee eeeeee ee eeeeeee ee eeeee eeee e eeeeeeeeeeeeee eeeeee ee eeeeeeeeeeeeeeeeeeee (‌88‌) ee eeee eeeeeeeeeee eee eee eeeeeee ee eeee eeeeee eeee eee eeeeee ee eeeeeeee eee eeeeeeeeeeeeee. Meeeeeeee eeeeeeeeeeeeee, eeeeeeeeeeeee ee eeeeeeeeeeeeee eeeeeeeee, eeee eeeeeeee eeee eee eeeeeeee ee eeeeeee ee eeeeee eee,[‌888‌] eeeeeeeee eeeeee,[‌888‌] eeeeeeee eeeee eeeeee,[‌888‌,‌888‌] eeeeeeee eeeeeeeee,[‌888‌] ee eeee eeeeeee eeeeee[‌888‌] eeeeeeeeeee eee eeeeeeee, eeeeeeee eee eeeeeeeeeee, eee eeeeeeee eeeeee eeeeee eeeee eeeeee eeeeeeeeee. Me eeee eeeee, eee eeeeeeee ee ee eeeeeeee ee e eeeeeeee eeeeee eee eee eeeeeeeee ee eeeeeeeeeeeeeee eeee eeee eeeeeeeeee ee eeeeee eeeee eeeeeee eeeeeeeeee.

Mee Meeeee–Meeee eeeeeeee ee eeeeee eeeeeeee ee eeee eeeeeeeeee eeeeee, eeeeeeeee eeeeee, eeeeeeee, eeeeeeee eeeeee, eeeeeeeeee, eeeeeee, eeeeee, eeeeee, eeeeee, eeeeeeee eeeee eeeeeeeee eeeeeee, eeeee, eee eeeeeeeee, eee eeee Meeeeee eeeeeee eeeeeeeee.[‌888‌,‌888‌] Mee eeeee ee eee eeeeeeee eeee eeeeeee ee eee eeeeeeeee eeeeeeeee ee eeee eeeeeeeeeeee. Meeee eeeeeee eeeeeeeeee, eee eeeeeee, eeeeee eeeeeeeeeee ee eeeeeeeee eeee, eeeeeeeeeee; eeeeeee, ee eeeee eee eeeeeeee eeeee M-eeeee eeeeeeee, eee eeeeeeee ee eeeeeeee ee eee eeeeee ee eeeeeeeeeee.[‌888‌] Meeeeeeee, eeeeee eeeeeeee eeeeeee eeeeeeeee eeeeeeeeeee, eee eeeeeeee eeeeeee eeeee eeee eeeeee ee eeee eeeeeeeeeeeeeee. Me eeeeeee eeeee, eeee ee eeeeeeee eeeeeeee eeeeeeeeee, eee eee ee eeeeeeeee ee eeeeeeeeee.

Me eeeeeeee, eee eeeee ee eee eeeeeeeeeeeeee eeeeeeee eeee eeeeeee ee eee eeeeee ee eeee eeeeeee (‌Meeeee 88‌). Meeeeeee eeeeee eeeeeee eee eee eeee eeeeeeeeee, eeeeeeeee eeeeeeee ee 88–88°M eeee e eeeeee ee eeeeeee eeeee. Meeeee eeeeeeeee eeeeee eee eeeeee eeee, eeeeeeeeeeee eee- eee eeeeeeeeeeeeeeee eeeeee eeeee eee eeeeee eeeee eeeeeeeeee eeeee eeeeeee eeeeeeeeeeee, eeeeeeeeee eeeeeee ee eeeeeeeeeeeeeee ee eee eeeeee. Meee eeeeeeeeee, eeeeeee eeeeeeeeee ee eeeeeeee-eeeeeeeeeee eeeeeeeeeeee eeeee eeee eeeeeeeeeee eee eeeeeee 8,8-eeeeee.[‌888‌] Meeeeeee, ee eee eeee eeeeeeee eeee eee eee ee M-eeeeeeeeeeeeeeee eeeee ee e eeeeeeee ee eee eeeeeeee eeeeee eee eeeeeeeee ee eeeeeeeeeeeeeee.[‌888‌] Meeeeee eeee eeee eeee eeeeeeee ee eeee eeeeeeee ee eee Meeeee–Meeee eeeeeeee.[‌888‌]

‌Meeeee 88‌ Meee Meeeeeee ee eee Meeeeeeeeeeeee Meeeee–Meeee Meeeeeee[‌888‌]

Meeeee eeeeeee eee eeeeeeeeee eeeeee eeeeeee eee eeee eeeeeeeee eeee eeeeeeeeee ee eeeeeeeeeeeeee eeeeeeeee. Meeeeeeeee eeee ee eeeeeeeeeeeeee eeeeeee eeeeeee eee Meeeee–Meeee eeeeeeee eeeeeeee ee eeee eeeeee. Meeeee, eee eeeeeeeeeeeeee eeeeeeee eee eeeee eee eeeee eeeeeeee eeeeeeeeeeee eeeeeee eee e eeeeee eeeeee. Meeeee ee eeeee eeeee ee eeee eeeee eeeeeeee eee eeeeee eee eeeeee eeeee eeeeeee eeee eeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeee (‌88‌) eee eeeeee eeeeeeeeee eeeeeee ee eeeeeeeee eeee eeeeeeeeeee eeeeeeeee ee eeee eee eeeeeeee eeeeee. Mee-8-ee-8-eee, eeeee eeeee eeeeeeee eeee e eeee-eeeeeeee eeee, eeeeeeeee eeeeee eeeeeeeeeeeeeeeeee eeeeeeeeeee.[‌888‌] Me eee eeeeeeee, eeeeeee[8.8.8]eee-8-ee-8-eeee, eee eeeeee ee eee eeeeeeeee ee eeeeeeee eeeeeeeeeeee-eeeee eeeeeeeeee eeeeeeeee, eee eeee eeeeeeeeeee eeeeeee eeeeeee eee eeeee eeeeeee eeee eeee-8-ee-8-eee. Mee eeeeeee eeee eeeeeeeeee ee eee eeeeeeeeeeeeeeeeeeee ee eee eeeeeeeeeeeeee eeeeeeeee, ee eeee ee eee eeeeeee ee eee eeeeeeeeeeee ee eeeeee eee ee eeeeeeee eeeee, eeee eee eeee eeeeeeee.[‌888‌,‌888‌–‌888‌] Mee eeeeeee ee eee eeeeeeeeeeee ee eee eeeeeeeeee eeee eeee e eeeeeeeee eeee ee ee eee eeeeeeeee eeeeeee eeeeeeeee ee eeee eeeeeeeeee eeeeeeeee eee eee eeeeeeeeeeeeee eeeeeeee. Meee ee ee eee eeeeeeeeeeeeee eeeeeee, eee eeeeeeeeeeeeee Meeeee–Meeee eeeeeeeee eee eeeeeee eee eeeee eeeeeee eeeeeeeeee. Me eeee eeeee, eeeeeeeee eeee eeeee eeeeee eeeeeeee eee eeeeeeee eeeee eee eeeeee eeeeeee eeeeeeeeeeeeeeeee eee eeeeeeee eeeeee. Me eee eeee eeee eeeeeeee eeee eee eeeeeeeeeeeeee eeeeeeee ee eeeeeeee-eeeeeeeee eeeeeee eeeeeeee eeeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeee eeeeeeeee ee eeee eeeee eeee eeeeeeeeeeee ee eeee ee eee eeeeeee.[‌888‌] Mee eeeeeeeeeeeeee eeeeeeee ee eee eeeeeee ee eeeeeee eee-eeeeee eeeeee. Meee, eee eeeeeeeee ee eeeeeee eeeeee eeeeeeeeee eeeeeeeeeee (eeeeee,[‌888‌] eeeeeeee,[‌888‌] ee eeeeee[‌888‌]) eeeeeee eee eeeeee eee eee eeeeee eeee ee eeee (‌Meeeee 88‌). Meeeeeeee eeeeeeeee eeeeee eeeeee eeee eeee eeee eeeeeeee eee, ee ee eeeeeeeeeeeeee eeeeeeee, eee [8+8+8] eeeeeeeeeeeee ee eeeeeeeee ee eeeee eeeeeeeee.[‌888‌,‌888‌]

‌Meeeee 88‌ Meeeeeee Meeeeeee ee eee Meeeeeeeeeeeee Meeeee–Meeee Meeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

Meeeeeeeee ee eeeeeee eeeeeeeeee eeeee- eee eeeeeeeeeeeeee Meeeee–Meeee eeeeeeeee eeee eeee eeeeeeeee. Mee eeeeeeeeee eee eee eee ee eeeeee eeeeeeeeeee eeeeeeee eeeee ee eeeeee ee eee eeeeeeeeeee eeeeeeee[‌888‌,‌888‌] ee eee eeeeeeeeee ee eeeeeeeee eeeeeeeeee e eeeeeeeeeee M8Me8 eeee; eeeeeee, eeee eee eeeee ee eeeee eee eeeee eeeeeeeeeee ee eee eeeeeeeee ee eeeeeee eeeeeeeee. Meee, eeee eeeeeeeeeeeeeeeeeeeeee (88% ee) eeee eeee eeeeeeee ee eeeee 88-(eeeeeeeeeeeee)eeeeeeeeee eeeeeeeeeee ee eeeeee eeeeeeeeeee (‌Meeeee 88‌). Meeeeeee, ee eee eeee eeeeeeeeeeee eeee eee eeeeeeee eeeee eee eeee ee eeee ee e eeee eeeeeeeee eeeeee eeeeeeeee. Meeeeeeeeee eeeeeeeeeeeeeeeee (>88% ee), eeeeeee eeee ee eeeeeeeee eeeee eeeeee eeeeeeeee eeeeeeeeeee eeee, eee eeeeeeeee.[‌888‌] Meeeeeeee eeee M-eeeeeeee-eeeee 8,8-eeeeee ee eeeeeeeeeeee eeeeeeeee eeee eeee eeee eeeeeeee ee eeeeee eee eeeeeeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeeeeeeeee eeee eeee.[‌888‌] Mee eee ee eeeeee eeeeeee eeee ee eee eeeeee eeeeeeeee eeeeee “eeeeeee” eee eeeeeeee eee eeee eeeeeeeeeeeeeee eeee eeeeeeee ee eeeeeeeee eeeeeeeeeeee eeeeee.[‌888‌,‌888‌] Mee eee ee eeeeee eeeeeeee eeeee eeeeee eee eeee eeeeeeee, eee eeee eeeeeee eeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeee Meeeeeee ee eee Meeeeeeeee Meeeee–Meeee Meeeeeee[‌888‌,‌888‌]

Meeeeeee eeee eeee eeee ee eeeeeee eee Meeeee–Meeee eeeeeeee eeeeeeeeeeeee, eeeee e eeeeee eeeeeeee eeeeeeeeee, eeee eeeeeeee eeeeeee. Meeeeeeee eeeeeeee eeeeeee eeee eeee eeeeeeeee eee eeeeee eee eeeeeeee eeeeeee eeee eeee eee ee eee eeeee ee eee eeeeeeee eee eeeeeee ee eee eee ee eeeeee ee eee eeeeee eeeeeee. Mee eeeee eeeeeeeee eeeeeeeee Meeeee–Meeee eeeeeeee eeeeeeee eeee eeeeeeeee eeeeeeeee ee eee eeeeeeee eee 8,8-eeeeeeeeeeeeeee ee eeeeeee (‌Meeeee 88‌); eee eeeeee eeee eeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eeeeeeee eee eeee eeeeeeeeeeeee eeeeeeee ee eeeeeeee eee eee eeeeeeee eeeee 8 eeeeeeeeeee ee eeeeee eeeeeeee.[‌888‌] Meeeeee eeeeeeeeeee eee eeeeeeeee eeeee 8,8-eeeeeeeeeeeeeee eeeeeeeeee eeee e eeeee eeeeee ee eeeee eeeee e eeeeeeee ee 8 eeeeeeeeeee ee eeeeee eeeeeeee.[‌888‌] Mee eeeeeeeee eeeeeee ee eee eeeeeeeeeeeeee eeeeeeee eee eeee eeee eeeeeeeee eeeee eeeeeeeeeee eeeee ee 88–88°M eeeee eeeeeee eeeeeeee ee eeeeee eeeeeeee, eee eeee eeeeee eeeeeeee eee eee ee eeee-eeeeee eeeeeeeeeeeeeeeeeeeee(8) (‌88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee Meeeeeee ee eee Meeeee–Meeee Meeeeeee[‌888‌–‌888‌]

Meee eeeeeeeeee eeeeeee eeee eeee eeeeeeeee eee eee eeeee- eee eeeeeeeeeeeeee Meeeee–Meeee eeeeeeee, eee eeee ee eee eeeeeee eee eee ee ‌88‌. Meeee eeeeeee: (8) e eeeeeeeee eeeeee eeeeeeeee e eeeeee(M) eeeeeee eeee ee eeeeeee eeeeee eee 8,8-eeeeeeeeeeeeeee ee eee eeeeeee eeeee 88 × 888 Meee ee eeeeee eeeeeeee,[‌888‌] (8) e eeeeee eeeeeeeee e eeeeeeeee eeeeee ee eee(eeeeeeeeeeeeeee)eeeeee(MM) eee eeeeee eeeeeeeeeee,[‌888‌] eee (8) e eeeeee eeeee e eeeeeeeeeeeeeeeee eeeeee ee eeeeee(MM) eeeeeee, eeee, eee eeeeee eeeeeeee (888 Meee) ee 88°M ee e eeeeeee ee eeee-eeeee eeeeeee eee eeeeeeeeeeeeeee.[‌888‌]

Meeeeee, eeeee ee eee eeeeeeeeeeee eeeeeeeeee, eee eeeeeeeeee eeeeeeeee, eee eee eeeeeeeeeee eeeee- eee eeeeeeeeeeeeee eeeeeee, eee Meeeee–Meeee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeeeeee eee ee eeeee eeeeeeeee; eeeeeee, eee eeeeeeeeeeee eee eee eeeeeeee ee ee eeeeeeeee eeee. Meeeee eee eeeeeeee e eeeeeeeeeeeee eeee ee ee 8888 ee eee eeeeee.[‌888‌] Mee eeeee eeeeeeeeeeee eeeee eeee eeee eeeeeee eee eeeeeeeee ee eeeee eeeeeeeee β-eeeeee eee eeeeeeeee eeeeeee,[‌888‌] eee eeeeeeeee ee eee eeeeeee eeeeeee,[‌888‌] ee eeeeeeee ee eeeeeeeeeeeeeeeeeee,[‌888‌] eee eeeee eeeeeeeee ee (+)-eeeeeeeeeeeeee,[‌888‌] ee eeeeeeeeee eeeeeeee ee (+)-β-eeeeeeeeee,[‌888‌] eee eee eeeeeeeee ee (±)-eeeeeeeeeeeeeeeeeeeeeeee.[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeee–Meeee Meeeeeeee; Meeeeee Meeeeeeee:[‌888‌,‌888‌]

Meeeee M: Meeeeee eeeeeeeeeeeeee eeeeeeeeeeee; eeeeeeeeeeeeee eeeeeeeeee.

Me e eeeeeee eeee ee eee eeeeeee (eeeeeeeee eeeeee eeeeeeeee eee eeeeee ee Meeeeee ‌8.8.8.8‌ ee ee eeee) (8 eeee) ee eeeeeee ee MMM (8 eM) eee eeeee eee eeeeee (8 eeee) ee eeeeeee ee MMM eeee (8 eM). Mee eeeeeee eee eeeeee ee 88–88°M eeeee eee eeeeee eeeeeee eeeeeeeeeee, ee eeeeeeeeee ee MMM eeeeeeee (88 e ee 8 e). Meeee eeeeeeeeee eeeeeee e eeeee eee ee eeeeee eee eee eeeeeee ee eee eeeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eeeeeeee eeee eee eeeeeee eeeeeeeeeeeeee eeeeeee eeeeeeeee eeeee eeeeeeeeeeeeee.

Meeeee M: MMM-eeeeeeee eeeeeeeeeeeeee eeeeeeeeeeee.

M eeee ee eee eeeeee eeeeeee (8.888 eeee) ee MM8Me8 (8 eM) eee eeeeeee eeee e eeeeee eeeeeee ee eeeee MMM (8.88 eeee, 8 eeeee) ee ee. Meeee 88 e ee ee, e eeeeee eeeeeeeeeee eee eeeeee, eee MMM eeeeeeee eeeeeeeee eee eeeeeeeeeee ee eee eee eeeeeeee eeeeeeee eeee eeeeeeeeeee eeeeeeeee ee e eeee eeeee eeeeeee. Mee eeeeeee eee eeeeee eeeeeee e eeeee eeee ee eeeeee eee eee eee eeeeeeee eee eeeeeeeeeeee ee eeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee ee eeeeee eee eeeeeeeeeeeee eeeeeeeeeeeeee.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88e, 8888.