Stereoselective Nucleophilic Additions to a Bicyclic Ketone Controlled by a Remote Tricarbonyl(diene)iron Moiety

Abstract

Electronic and not steric factors are the cause of the stereoselective course of the reduction of the ketone 1 with hydrides to give the alcohol 2. The Fe(CO)3 group favors the preferred syn‐attack of the nucleophile (Z, RH).

Circular Dichroism of Tricarbonyl(diene)iron Complexes. The Octant Rule Applied to Ketones Perturbed by Remote Fe(CO)3 Groups. Crystal Structure of (±)‐Tricarbonyl[(1RS,4RS,5RS,6SR)‐C5,6,C‐η‐(5,6,7,8‐tetramethylidene‐2‐bicyclo[2.2.2]octanone)]iron

“…130 (7) 1.14(1) I. 127 (9) 1.393 (9) 38.6 (3) (4) 177.6(7) 178.9 (7) 95.3 (3) 99.3 (4) 178.3 (9) 0.5 (9) C(3)-C(4)-C( I )-C (2) 0.6(9) C(4)-C(3)-C(2)-0(1) -179.2 (9) The crystal structure of (f)-8 does not provide us with an explanation based on ground-state properties of this molecule for the stereoselectivity of the H/D exchange 8-12 [l 11 and the stereoselective hydride reductions of (*)-8 [20]. Our results suggest in fact that the face of the ketone function syn to the complexed diene moiety is less available on steric grounds than the other face.…”

Remote Tricarbonyl(diene)iron Substituent Effect on Ester Heterolysis. The Solvolyses of 5,6,7,8‐Tetramethylidenebicyclo[2.2.2]oct‐2‐yl Methanesulfonate and of its Tricarbonyliron Mono‐ and Dinuclear Complexes

“…The mesylates 17-23 were derived from the corresponding alcohols 24-30 using standard procedures (CH,SO,Cl/pyridine). The preparations of alcohols 24, 25 [18], 27 [19] [20], 28 [19], 29, and 30 [18] have already been described. Alcohol 26 was prepared by selective oxidation of the doubly complexed tetraenol 30 with Me,NO in anhydrous acetone [21].…”