TY - JOUR
T1 - Facial Selectivity in Mechanical Bond Formation
T2 - Axially Chiral Enantiomers and Geometric Isomers from a Simple Prochiral Macrocycle
AU - Gallagher, Peter R.
AU - Savoini, Andrea
AU - Saady, Abed
AU - Maynard, John R.J.
AU - Butler, Patrick W.V.
AU - Tizzard, Graham J.
AU - Goldup, Stephen M.
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/4/3
Y1 - 2024/4/3
N2 - In 1971, Schill recognized that a prochiral macrocycle encircling an oriented axle led to geometric isomerism in rotaxanes. More recently, we identified an overlooked chiral stereogenic unit in rotaxanes that arises when a prochiral macrocycle encircles a prochiral axle. Here, we show that both stereogenic units can be accessed using equivalent strategies, with a single weak stereodifferentiating interaction sufficient for moderate to excellent stereoselectivity. Using this understanding, we demonstrated the first direct enantioselective (70% ee) synthesis of a mechanically axially chiral rotaxane.
AB - In 1971, Schill recognized that a prochiral macrocycle encircling an oriented axle led to geometric isomerism in rotaxanes. More recently, we identified an overlooked chiral stereogenic unit in rotaxanes that arises when a prochiral macrocycle encircles a prochiral axle. Here, we show that both stereogenic units can be accessed using equivalent strategies, with a single weak stereodifferentiating interaction sufficient for moderate to excellent stereoselectivity. Using this understanding, we demonstrated the first direct enantioselective (70% ee) synthesis of a mechanically axially chiral rotaxane.
UR - http://www.scopus.com/inward/record.url?scp=85186604195&partnerID=8YFLogxK
U2 - 10.1021/jacs.3c14329
DO - 10.1021/jacs.3c14329
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C2 - 38507717
AN - SCOPUS:85186604195
SN - 0002-7863
VL - 146
SP - 9134
EP - 9141
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 13
ER -