Synthesis of C-aryl-Δ2,3-glycopyranosides via uncatalyzed addition of triarylindium reagents to glycals

2,6-Di(4-t-butylphenyl)phenyl-group 13 organometallic compounds

“…Correspondingly, other R 2 GaX compounds (R = 2,6-Ph 2 C 6 H 3 ; X = I [16], and R = 2,6-Mes 2 C 6 H 3 ; X = Cl [22], Br [14]), all have distorted trigonal planar environments around the gallium metal center. The C-Ga-Br bond angles in With the growing utility of triorganoindium compounds for fundamental organic transformations such as conjugate addition [23], cross-coupling [24][25][26], and allylic substitution reactions [27,28], and the ubiquitous use of m-terphenyl ligands in organometallic-group 13 chemistry, it is noteworthy that there are no reports of tris(m-terphenyl)indium compounds. Compound 4, the first tris (m-terphenyl)group 13 compound, is noteworthy.…”

“…The three ligands in 4 are arranged about the indium atom in a propeller like fashion and are not crystallographically equivalent due to differing dihedral angles with respect to the InC 3 -core plane. The dihedral planes were found to be 39.84°, 31.95°, and 65.37°for the C(1), C(27) and C(53) central phenyl ring planes, respectively. TheIn-C bonds in 4 (In(1)-C(1), 2.200(3) Å ; In(1)-C(27), 2.199(3) Å ; In(1)-C(53), 2.193(3) Å ) are comparable to those in Mes 3 In (2.170(5) Å ; 2.170(5) Å ; 2.163(5) Å ), Ph 3 In (2.111(14) Å ; 2.155(14) Å ), and (2,6-Mes 2 C 6 H 3 ) 2 InBr (2.171(25) Å ; 2.166(26) Å )…”

Recent Developments in the Ferrier Rearrangement

“…Triaryl‐, trivinyl‐, and tris(alkynyl)indium reagents react with C3‐acetyl glycals in Et 2 O at room temperature to give C ‐aryl, C ‐vinyl, and C ‐alkynyl Δ 2,3 ‐glycosides, of predominantly α‐configuration, in good yields 203. In these reactions, indium(III) is believed to act as a Lewis acid assisting in the departure of the C3 acetate.…”

The synthesis of d-C-mannopyranosides

“…As part of their synthesis of 2,3-unsaturated-C-aryl glycopyranosides, Price et al also reported that dihydroxylation is efficient even with simple acetate protecting groups [256].…”