✦ LIBER ✦
Electron transfer photochemistry of 7-(spirocyclopropane)quadricyclane: capture of a radical cation and sequential cyclopropylcarbinyl rearrangements
✍ Scribed by Sean McIlroy; Hengxin Weng; Heinz D. Roth
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 76 KB
- Volume
- 10
- Category
- Article
- ISSN
- 0894-3230
No coin nor oath required. For personal study only.
✦ Synopsis
The electron transfer photo-sensitized reaction of 7-(spirocyclopropane)quadricyclane (1) with methanol produces two rearranged mono-methanol adducts, 2 and 3, and a bis-methanol adduct, 4. The products reveal that 1 ᭹ + reacts by stereo-and regiospecific attack of methanol on one trisubstituted cyclopropane ring. The resulting free radical rapidly undergoes one or two (consecutive) cyclopropylcarbinyl to butenyl rearrangements. The mono-adducts are formed by net hydrogen abstraction, the di-adduct via a (secondary) electron transfer reaction of 3.