Diastereoselective Allylations of Enantiopure 3- and 4-Substituted η⁴-(1Z)-(Sulfinyldienal)iron(0) Tricarbonyl Complexes

Abstract

Diastereoselectivity of allylations of enantiopure 3- and 4-substituted η4-(1Z)-(sulfinyldienal)iron(0) tricarbonyl complexes is dependent on the nature of the alkyl substituent. For 1-sulfinyl-1,3-pentadien-5-al iron complexes (11a−d), the aldehyde predominately reacts through the s-cis conformer, with diastereoselectivites as high as 95:5 (for homoallylic alcohol 13d). For 3-formyl-1-sulfinyl-1,3-butadiene iron complexes (12a,b), the aldehyde predominately reacts through the s-trans conformer (diastereomer ratio for homoallylic alcohol, 14b, 89:11).

Recent Developments in the Synthesis and Utilization of Chiral Sulfoxides

“…These include the synthesis of chiral ferrocenyl sulfoxides, η 6 -sulfinyl arene−Cr(CO 3 ) complexes, η 4 -(3-sulfinyl enone)−Fe(CO) 3 complexes, and finally, η 4 -sulfinyl diene−Fe(CO) 3 . The groups of Paley and Fernández de la Pradilla reported on the stereoselective synthesis of η 4 -sulfinyl diene−Fe(CO) 3 and their utilization in asymmetric synthesis. − As a first part of this work, various efficient strategies directed toward the synthesis of enantiopure sulfinyl dienes, either E or Z, 288 and 289 (Scheme ), were developed . This was achieved via Stille coupling of halovinyl sulfoxides and vinyl stannanes, hydrogenation of 1-sulfinyl-1-en-3-ynes, or vinylcupration of 1-sulfinyl alkynes .…”

Planar-to-Axial Chirality Relay in Phospharuthenocenes. A Rotationally Hindered 2-(2‘-Diphenylphosphinonaphth-1‘-yl)phospharuthenocene

“…The highly deshielded protons found in compounds 4 , 5 , and 6 , (δ 1 H = 9.79, 9.66, and 9.39 ppm for H-8 in C 6 D 6 , respectively) lie close to the value in the crystallographically established 1a and confirm exo conformations. However, the chemical shift (δ 1 H = 7.54 ppm in CDCl 3 ) for H-8 in 3 , containing the smaller OH substituent, clearly indicates an endo configuration, and this was confirmed for the solid state by a crystal structure analysis (Figure ) …”

Synthesis, structure and dynamics of methoxynaphthalene-substituted phospha-ruthenocenes and -ferrocenes

“…The hydroxyl hydrogen atom was located in the final difference map and is oriented away from the iron atom, so the naphthyl orientation does not result from an O-H • • • Fe interaction. 44, 45 Rotating the C-C bond to allow maximum coplanarity between the phospholyl and naphthyl groups gives minimum distances from the C(3) methyl group of 1.66 A ˚to C(13) and 1.84 A ˚to O(1).…”