| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2000: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Research Abstract |
1. Dehydrogenative Silylation of Amines and Hydrosilylation of Imines Catalyzed by Ytterbium-Imine Complexes. Dehydrogenative silylation of primary and secondary amines with triphenylsilane was catalyzed by ytterbium-imine complexes, [Yb(η^2-Ph_2CNAr)(hmpa)_n], to give aminosilanes in good yields. In the reaction with diphenyland phenylsilanes, diaminosilanes were formed as major products. While n- and sec-alkylamines were readily silylated, tert-alkylamines and aromatic amines exhibited lower reactivities. Moreover, hydrosilylation of imines has been achieved by using phenylsilane and the imine complexes (At=Ph, C_6H_4F-4), giving rise to mono- and diaminosilanes. The two reactions were in agreement as regards the product selectivities and yields.
2. Three-Component Coupling of Acylphosphonates and Two Carbonyl Compounds Promoted by Low-Valent Samariums : One-Pot Synthesis of β-Hydroxyphosphonates. Three-component coupling of acylphosphonates and two carbonyl compounds leading to β-hydroxyphosphonates has been achieved with low-valent samariums. Thus, acylphosphonates reacted with aldehydes in the presence of semi-catalytic amounts of samarium metal or SmI_2 to give acyloxyphosphonates -in good yields. The second coupling reaction of the acyloxyphosphonates with aldehydes or ketones promoted by SmI_2 afforded β-hydroxyphosphonates, instead of olefins. Moreover, these two reactions could be carried out in one pot.
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