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36.5.1.20.1 Variation 1: Achiral Catalytic Alkenylations of Carbonyl Compounds

DOI: 10.1055/sos-SD-036-00485

Hodgson, D. M.; Humphreys, P. G.Science of Synthesis, (200836631.

Intramolecular alkylative or reductive couplings between terminal or substituted alkynes and aldehydes are possible using a nickel catalyst, such as bis(cycloocta-1,4-diene)nickel, which gives cyclic allylic alcohols containing stereochemically defined exocyclic di-, tri-, or tetrasubstituted alkene units (Scheme 51).[‌216‌,‌271‌] The elegance of this chemistry arises from the careful choice of reagents that allow the formation of whichever alkene isomer is required. Thus, nickel-catalyzed reductive intramolecular cyclization of a terminal alkyne to give the Z-trisubstituted allylic alcohol 105 is possible with the addition of an organolithium. With a substituted alkyne, intramolecular reductive cyclization in the presence of a trialkylphosphine allows the synthesis of an E-trisubstituted allylic alcohol 106, whereas the addition of a Grignard reagent in the last reaction allows access to a tetrasubstituted allylic alcohol 107 of defined geometry. Typically five- or six-membered rings are formed, although there are examples of macrocyclizations of this type giving up to 22-membered rings in yields of 6070%.[‌272‌]

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