What I Wish Everyone Knew About 1,1′-Diacetylferrocene

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Treatment of [Fc-1-R1-1?-R2] (R1 = H, R2 = CH(O); R1 = H, R2 = CMe(O); R1 = R2 = CMe(O)) with LiC{triple bond, long}CCH2OLi (prepared in situ from HC{triple bond, long}CCH2OH and n-BuLi) affords the ferrocenyl-substituted but-2-yne-1,4-diol compounds of general formula [Fc-1-R1-1?-{CR(OH)C{triple bond, long}CCH2OH}] (R1 = R = H (1a); R1 = H, R = Me (1b); R1 = CMe(O), R = Me (1c)) in low to high yields, respectively (where Fc = Fe(eta5-C5H4)2). In the case of the reactions of [Fc-1-R1-1?-R2] (R1 = H, R2 = CH(O); R1 = R2 = CMe(O)), the by-products [Fc-1-R1-1?-{CR(OH)(CH2)3CH3}] (R1 = R = H (2a); R1 = CMe(O), R = Me (2c)) along with minor quantities of [Fc-1,1?-{CMe(OH)(CH2)3CH3}2] (3) are also isolated; a hydrazide derivative of dehydrated 2c, [1-(CMe{double bond, long}CHCH2CH2CH3)-1?-(CMe{double bond, long}NNH-2,4-(NO2)2C6H3)] (2c?), has been crystallographically characterised. Interaction of 1 with Co2(CO)8 smoothly generates the alkyne-bridged complexes [Fc-1-R1-1?-{Co2(CO)6-mu-eta2-CR(OH)C{triple bond, long}CCH2OH}] (R1 = R = H (4a); R1 = H, R = Me(4b); R1 = CMe(O), R = Me (4c)) in good yield. Reaction of 4a with PhSH, in the presence of catalytic quantities of HBF4 · OEt2, gives the mono- [Fc-1-H-1?-{Co2(CO)6-mu-eta2-CH(SPh)C{triple bond, long}CCH2OH}] (5) and bis-substituted [Fc-1-H-1?-{Co2(CO)6-mu-eta2-CH(SPh)C{triple bond, long}CCH2SPh}] (6) straight chain species, while with HS(CH2)nSH (n = 2,3) the eight- and nine-membered dithiomacrocylic complexes [Fc-1-H-1?-{cyclo-Co2(CO)6-mu-eta2-CH(S(CH2)n-)C{triple bond, long}CCH2S-}] [n = 2 (7a), n = 3 (7b)] are afforded. By contrast, during attempted macrocyclic formation using 4b and HSCH2CH2OCH2CH2SH dehydration occurs to give [Fc-1-H-1?-{Co2(CO)6-mu-eta2-C({double bond, long}CH2)C{triple bond, long}CCH2OH}] (8). Single crystal X-ray diffraction studies have been reported on 2c?, 4b, 4c, 7b and 8.

In the meantime we’ve collected together some recent articles in this area about 1273-94-5 to whet your appetite. Happy reading! Electric Literature of 1273-94-5

Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion