You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via3.6.2.4.1.1 Unactivated Alkenes as Ene Components
Please login to access the full content or check if you have access via
Terada, M., Science of Synthesis: Stereoselective Synthesis, (2011) 3, 341.
The ene reaction of an azodicarboxylate with unactivated alkenes provides a novel route to allylic amines; however, the enantioselective variant has received little attention. The first reported enantioselective ene reaction used the oxazolidine-derived azodicarboxylate enophile analogue 74 with 1,2-di- and 1,1,2-trisubstituted alkenes to provide a regioisomeric mixture of hydrazines 75 and 76 using the chiral copper(II) complex ent-35 (Scheme 27).[112] The product ratio is strongly dependent upon the alkene substitution pattern, and a trisubstituted alkene gives exclusive formation of hydrazine 76 with the highest enantioselectivity (60% ee). The enantioselective ene reaction using nitroso compounds as enophiles with unactivated alkenes has also been reported using a copper(I) catalyst with a chiral diphosphine ligand; however, the enantioselectivity is moderate (up to 40% ee).[113]
Meeeee 88 Meeeeeeeeeeeeeee Mee Meeeeeee ee ee Meeeeeeeeeeeeeee Meeeeeee eeee Meeeeeeeeee Meeeeee Meeeeeeee ee e Meeeee Meeeee(MM) Meeeeee[888]
| M8 | M8 | M8 | Meee (e) | Meeee (88/88) | ee (%) ee 88 | ee (%) ee 88 | Meeee (%) | Mee |
|---|---|---|---|---|---|---|---|---|
| (MM8)8 | M | 88 | >88:8 | 88 | – | 88 | [888] | |
| Me | (MM8)8 | 88 | 8:>88 | – | 88 | 88 | [888] | |
| Me | Me | M | 88 | 88:88 | 8 | 88 | 88e | [888] |
e Meeeeeee eeeeee eee ee M-eeeeeeeeeeeee.
Meeeeeeeeeee Meeeeeeee
8,8,8-Meeeeeeeeeeeee 8-Meeee-8-(8-eeeeeeeeeeeeee-8-eeeeeeee)eeeeeeeeeeeeeeeeeeeee 88 eee 8,8,8-Meeeeeeeeeeeee 8-Meeee-8-(8-eeeeeeeeeeeeee-8-eeeeeeee)eeeeeeeeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[888]
Me(MMe)8 (88.8 ee, 8.8 eeee) eee (8M,8′M)-8,8′-(eeeeeee-8,8-eeee)eee(8-eeeeee-8,8-eeeeeeeeeeeeee) (88.8 ee, 8.88 eeee) eeee eeeee ee ee eeee-eeeee Meeeeee eeee eeeeeeee eeee e eeeeeeee eeeeeee eee. Mee eeeeeee eee eeeeeee eeeee eeeeee eee 8 e eee eee eeee eee eeee eeeeee eeee M8. Mee MM8Me8 (8 eM) eee eeeee eee eee eeee eee eeeeeee eee 8 e ee eeee eeeeeeee eee-88. Meeeeeeeeeeeeeee eeeeeeee 88 (888 ee, 8.8 eeee) eee eeee eeeee, eeeeeeee ee eee eeeeee (8 eeee) eee eee eeeeeee eee eeeeeee ee ee eee eee eeeeeeeeeee eeee. Mee eeeeeee eee eeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MM8Me8/MeMMe 8:8).
References
| [112] | Meeeee, M. M.; Meeeee, M.; Meeeee, M. M.; Møeeeeeee, M. M., Mee. Meeeee. Meee., (8888) 8, 8888. |
| [113] | Meee, M.; Meeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 888. |
Return to Top