Selective Monofunctionalization Enabled by Reaction‐History‐Dependent Communication in Catalytic Rotaxanes
Abstract
Selective monofunctionalization of substrates with distant, yet equally reactive functional groups is difficult to achieve, as it requires the second functional group to selectively modulate its reactivity once the first functional group has reacted. We now show that mechanically interlocked catalytic rings can effectively regulate the reactivity of stoppering groups in rotaxanes over a distance of about 2 nm. Our mechanism of communication is enabled by a unique interlocked design, which effectively removes the catalytic rings from the substrates by fast dethreading as soon as the first reaction has taken place. Our method not only led to a rare example of selective monofunctionalization, but also to a “molecular if function”. Overall, the study presents a way to get distant functional groups to communicate with each other in a reaction‐history‐dependent manner by creating linkers that can ultimately perform logical operations at the molecular level.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Jul 22, 2020
- Source ID
- 10.1002/ange.202006305
Entities
People
- Dillon R. Mccarthy
- Jianing Li
- Jonathon B. Ferrell
- Joseph P. Campbell
- Mona Sharafi
- Ona Ambrozaite
- Severin T Schneebeli
- Sinu C Rajappan
Organizations
- American Chemical Society Petroleum Research Fund
- Army Research Office
- National Institute of General Medical Sciences
- National Institutes of Health
- Nvidia
- University of Vermont