Science of Synthesis

Mase, N., Science of Synthesis Knowledge Updates, (2013) 3, 337.

Regio- and enantioselective vinylogous amination of methyl 2-cyanoalk-2-enoates ‌86‌ (R1 = CO2Me) and alkylidenemalononitriles ‌86‌ (R1 = CN) with azodicarboxylates represents a powerful and versatile method for the asymmetric construction of stereogenic centers bearing C—N bonds to afford highly functionalized α,β-unsaturated γ-aminonitriles ‌87‌. Enantioselectivities of up to 99% ee are observed using the commercially available organocatalyst ‌57B‌ (‌Scheme 22‌).[‌86‌]

‌Meeeee 88‌ Meeeeeeeee Meeeeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeeeeee eeeeeeeee ee 8 °M eee 88 e.

Meeeeeeeeeee Meeeeeeee

Me-eeee-eeeee (M)-8-(8-Meeee-8-eeeeeee-8-eeeeee-8-ee-8-ee)eeeeeeeee-8,8-eeeeeeeeeeeeee ‌88‌ (M8 = MM8Me; M8 = M, Me; M8 = Meeee); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee eeee eeeeeeee eeee e eeeeeeee eeeeeee eee eeee eeeee MM8Me8 (8.8 eM), ee-eeee-eeeee (M)-eeeeeeeeeeeeeeee (88.8 ee, 8.88 eeee), eee eee eeeeee 8-eeeeeeee-8-eeeeee ‌88‌ (M8 = MM8Me; M8 = M, Me; M8 = eeeee; 8.8 eeee). Mee eeee eeee eee eeeeee eeee e eeeeee eeeeee, eee eee eeeeeee eee eeeeeee ee ee ee eeeeeeee eee eeeeee eee eeee eeeeee ee −88 °M. Meeeeeeeeeeeee ‌88M‌ (88.8 ee, 8.88 eeee, 88 eee%) eee eeeee ee e eeeee ee eee eeeeee eeeeeee, eeeee eee eeee eeeeee ee −88 °M eee 88–88 e. Mee eeeeeee eee eeee eeeeee ee −88 °M eee eeeeee eeeeeeee eeee e eeeeeeeeeeeeee eeeeee eeeeeeeeee Meeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee; eeeee: 88–88%; 88–88% ee.

References