Cyclopentadienyl‐Free Rare‐Earth Metal Amides [{(CH 2 SiMe 2 ){(2,6‐ i Pr 2 C 6 H 3 )N} 2 }Ln{N(SiMe 3 ) 2 }(THF)] as Highly Efficient Versatile Catalysts for C–C and C–N Bond Formation

Efficient methods have been developed for the direct synthesis of amides from aldehydes and a straightforward route to propiolamidines using cyclopentadienyl‐free rare‐earth metal amides [{(CH 2 SiMe 2 ){(2,6‐ i Pr 2 C 6 H 3 )N} 2 }Ln{N(SiMe 3 ) 2 }(THF)] [Ln = Yb ( 1 ), Y ( 2 ), Dy ( 3 ), Sm ( 4 ), Nd ( 5 )] as versatile catalysts. The results indicate that in the direct synthesis of amides from aldehydes the catalysts have the activity order 2  >  1    3    4    5 . These methods have the advantage of easy preparation of the catalysts, low catalyst loading, high conversion of substrates to products, mild reaction conditions, and compatibility with a wide range of substrates.