Preparation and chiroptical properties of optically active vinyl ether-iron and olefin-iron complexes. A CD quadrant rule correlating absolute configurations

New chemical and stereochemical applications of organoiron complexes

“…Optically active metal-alkene complexes in which the alkene itself is a center of asymmetry provide unique substrates for asymmetric carbon-carbon bond-formation [ 14 ]. Recently, Rosenblum et al [ 37 – 40 , 482 ] reported the preparation of the optically active iron complex 315, which serves both as a unique platform for asymmetric C–C bond-formation and for the preparation of optically active alkyl vinyl ether-iron complexes in which the exclusive locus of asymmetry is the alkene center. Complex 316 adds nucleophiles of a broad range of basicities (e.g., NaBH 3 CN, PhMgBr, PhCH 2 SH, etc.)…”

“…Recently, a promising dynamic resolution of vinyl ether-iron complexes has been reported by the same group [ 40 ]. Thus, optically active vinyl ether-iron complexes (a prototype of 320) can be readily generated from the racemic ethyl vinyl ether-iron complexes by alkoxy exchange with optically active alcohols.…”

“…The credit for the development and application of organoiron complexes in organic and organometallic chemistry can be ascribed to brilliant contributions by Fischer [ 32 , 33 ], Pettit [ 34 ], Müller [ 35 ], Alper [ 10 ], King [ 36 ], Rosenblum [ 37 – 40 ], Brunner [ 41 ], Birch [ 14 ], Collman [ 42 ], Gompper [ 43 ], Sarel [ 44 ], Noyori [ 45 , 46 ], Pearson [ 20 , 21 ], Casey [ 47 ], Hegedus [ 13 ], Wojcicki [ 48 ], Reger [ 49 ], Helquist [ 50 ], Gladysz [ 51 ], Kerber [ 52 ], Wulff [ 53 ], Ojima [ 54 ], Negishi [ 55 ], Backvall [ 56 ], Herndon [ 57 ], von Gustorf [ 58 ], Grée [ 30 ], Seyferth [ 59 ], Davies [ 60 – 63 ], Liebeskind [ 64 ], Semmelhack [ 65 ], Brookhart [ 66 ], and others [ 31 , 67 – 73 ]. Credit is also due Fischer [ 24 ], Dötz [ 74 ], Jaouen [ 18 ], Semmelhack [ 19 ], Wulff [ 53 , 75 ] Hegedus [ 76 ], Yamashita [ 77 ], and others [ 77a , 77b ] for their st...…”

Enolate Additions to a Chiral 3-Hydroxypropionate 2,3-Dication Equivalent. Enantioselective Synthesis of β,δ-Dihydroxy Esters

“…Complex 2 has been converted to the optically active dioxino complexes 3 and 4 , through exchange etherification with ( S )-propane-1,2-diol and ( R , R )-butane-2,3-diol, respectively (Figure ), and these have been used in the preparation of complexes 1a,b in optically active form . We have also shown that the absolute configurations of Fp-(vinyl ether) and vinylene diether complexes may be assigned through application of a simple CD quadrant rule …”