We describe the stereoselective synthesis of highly functionalized 1-substituted (E)-1,3-dienes by reductive β-elimination of 2-chloroallyl acetates, derived from the indium-promoted allylation of aldehydes with 1,3-dichloropropene and subse-

S y n t h e s i s o f ( E ) -a , b -U n s a t u r a t e d E s t e r s w i t h T o t a l S t e r e o s e l e c t i v i t yAbstract: Synthesis of (E)-a,b-unsaturated esters in high yields and with total stereoselectivity is achieved from a-halo-b-hydroxy esters promoted by catalytic amounts of SmI 2 . The starting compounds were easily prepared from a-halo esters and aldehydes as a mixture of stereoisomers. A mechanism is proposed to explain this samarium(II)-promoted catalytic b-elimination reaction.

The synthesis of β-amino esters or amides has been achieved from moderate to high yields from the reaction of imines and α-halo esters or amides promoted by catalytic amounts of samarium diiodide in the presence of magnesium turnings as coreductant. A mechanism is proposed to explain this catalytic samarium(II)-promoted aza-Reformatsky reaction.

Synthesis of Highly Functionalized Enantiopure Halocyclopropanes Derived from Carbohydrates. -The title synthesis can be stereospecifically carried out on E-or Z-α,β-unsaturated amides. A mechanism is proposed. -(RODRIGUEZ-SOLLA*, H.; CONCELLON, C.; DEL AMO, V.; DIAZ-PARDO, A.; BLANCO, E. G.; GARCIA-GRANDA, S.; DIAZ, M. R.; LLAVONA, R.; SOENGAS, R. G.; Eur. J. Org. Chem. 2013, 22, 4953-4961, http://dx.

Aza-Reformatsky Reaction Promoted by Catalytic Samarium Diiodide: Synthesis of -Amino Esters or Amides. -(RODRIGUEZ-SOLLA*, H.; DIAZ-PARDO, A.; CONCELLON, C.; DEL AMO, V.; Synlett 25 (2014) 12, 1709-1712, http://dx.