An efficient nickel-catalyzed alkenylation of functionalized benzylic halides with alkenylaluminum reagents.

Highly efficient and simple coupling reactions of benzylic bromides or chlorides with alkenylaluminum reagents catalyzed by NiCl(2)(PPh(3))(2) are reported. The coupling reactions proceed effectively at room temperature employing low loading of catalyst, 0.5 mol% for benzylic bromides having either electron-donating or -withdrawing substituents on the aromatic ring, affording coupling products in excellent yields of up to 94% in short reaction times.

Simple and efficient nickel-catalyzed cross-coupling reaction of alkynylalanes with benzylic and aryl bromides.

Highly efficient and simple coupling reactions of benzylic and aryl bromides with aluminium acetylide catalyzed by NiCl(2)(PPh(3))(2) are reported. The coupling reactions proceed at room temperature employing 4 mol% catalyst, affording coupling products in excellent yields of up to 95% in short reaction times. The system worked efficiently with aryl and heterocyclic bromides as well.

Direct asymmetric catalytic thienylaluminum addition to ketones: a concise approach to the synthesis of (S)-tiemonium iodide.

A direct asymmetric addition of a (2-thienyl)aluminum reagent to ketones catalyzed by a titanium catalyst of (S)-BINOL to afford chiral tertiary 2-thienyl alcohols is reported. The catalytic system works excellently for aromatic ketones and for 1-acetylcyclohexene, furnishing products in excellent enantioselectivities of up to 97% ee. However, the additions to dialkyl ketones afford products in low enantioselectivities of 8-17% ee.

Highly enantioselective vinyl additions of vinylaluminum to ketones catalyzed by a titanium(IV) catalyst of (S)-BINOL.

We report a novel asymmetric addition of vinyl group to ketones using vinylaluminum reagents catalyzed by in situ prepared Ti(O(i)Pr)(4) complexes of (S)-BINOL to afford diversified tertiary allylic alochols. Varieties of aromatic ketones bearing either an electron-donating or an electron-withdrawing substituent on the aromatic ring were examined to afford products in excellent enantioselectivities of up to 98% ee with high yields. A 10-fold scale-up reaction afforded the product in a similar yield with a comparable enantioselectivity.