Catalytic Enantioselective Allylation of Ketones via a Chiral Indium(III) Complex

Abstract

[reaction: see text] A chiral indium complex has been discovered to effect high enantioselectivities in the addition of allyltributylstannanes to ketones. The allylation of a variety of aromatic, alpha,beta-unsaturated and aliphatic ketones resulted in good yields and high enantioselectivities (up to 92% ee).

Total Syntheses and Biological Evaluation of Both Enantiomers of Several Hydroxylated Dimeric Nuphar Alkaloids

“…After considerable experimentation, we identified In(OTf) 3 /(3R,8S)-22 as the optimal Lewis acid-ligand [15][16][17] combination for generating (+ +)-15 (corresponds to the thiobinupharidine configuration; entry 16), whereas Cu(OTf) 2 alone gave predominantly (À)-17 (corresponds to the neothiobinupharidine configuration; entry 1). Theproducts obtained are bis-nitriles 15-18.T he assignment of the stereochemical configuration at C7/C7' was accomplished by converting them to the corresponding fully reduced compounds 1d, 2d, 3d,a nd 4d,w hich were then compared with literature data.…”

“…Theproducts obtained are bis-nitriles 15-18.T he assignment of the stereochemical configuration at C7/C7' was accomplished by converting them to the corresponding fully reduced compounds 1d, 2d, 3d,a nd 4d,w hich were then compared with literature data. After considerable experimentation, we identified In(OTf) 3 /(3R,8S)-22 as the optimal Lewis acid-ligand [15][16][17] combination for generating (+ +)-15 (corresponds to the thiobinupharidine configuration; entry 16), whereas Cu(OTf) 2 alone gave predominantly (À)-17 (corresponds to the neothiobinupharidine configuration; entry 1). Under these conditions,w ec ould obtain synthetically useful amounts of all stereoisomers 15-18.T he use of chiral phosphoric acids or catalytic amounts of Lewis acids was not optimal.…”

Chalcogenoacetylenes Obtained by Indium(III) Catalysis: Dual Catalytic Activation of Diorgano Dichalcogenides and Csp–H Bonds

“…As green Lewis acid catalysts they have been extensively investigated. [20] For example, indium(III) was used in Diels-Alder, [21] FriedelCrafts, [22] Mukaiyama aldol, [23] and Hosomi-Sakurai allylation reactions. [24] Recently, Wang et al described the arylation of diorgano diselenides with arylboronic acids catalyzed by indium(III).…”

Chiral imine copper chloride-catalyzed enantioselective desymmetrization of 2-substituted 1,2,3-propanetriols

“…Although the chiral functionality has been often installed through asymmetric epoxidation (4)(5)(6) and dihydroxylation (7,8), several enantioselective methodologies have emerged in recent years, such as cyanohydrin formation (9)(10)(11)(12)(13)(14)(15)(16)(17)(18), organometallic addition (19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38), aldol condensation (39)(40)(41)(42) and epoxide opening (43)(44)(45). Because most of the reported methods have their own limit of application, it is worthwhile to expand the functionalization scope, especially in terms of the substrate diversity.…”