Robust,
Chiral, and Porous BINAP-Based Metal–Organic
Frameworks for Highly Enantioselective Cyclization Reactions
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Abstract
We
report here the design of BINAP-based metal–organic frameworks
and their postsynthetic metalation with Rh complexes to afford highly
active and enantioselective single-site solid catalysts for the asymmetric
cyclization reactions of 1,6-enynes. Robust, chiral, and porous Zr-MOFs
of UiO topology, BINAP-MOF (<b>I</b>) or BINAP-dMOF (<b>II</b>), were prepared using purely BINAP-derived dicarboxylate linkers
or by mixing BINAP-derived linkers with unfunctionalized dicarboxylate
linkers, respectively. Upon metalation with Rh(nbd)<sub>2</sub>BF<sub>4</sub> and [Rh(nbd)Cl]<sub>2</sub>/AgSbF<sub>6</sub>, the MOF precatalysts <b>I</b>·Rh(BF<sub>4</sub>) and <b>I</b>·Rh(SbF<sub>6</sub>) efficiently catalyzed highly enantioselective (up to 99%
ee) reductive cyclization and Alder-ene cycloisomerization of 1,6-enynes,
respectively. <b>I</b>·Rh catalysts afforded cyclization
products at comparable enantiomeric excesses (ee’s) and 4–7
times higher catalytic activity than the homogeneous controls, likely
a result of catalytic site isolation in the MOF which prevents bimolecular
catalyst deactivation pathways. However, <b>I</b>·Rh is
inactive in the more sterically encumbered Pauson–Khand reactions
between 1,6-enynes and carbon monoxide. In contrast, with a more open
structure, Rh-functionalized BINAP-dMOF, <b>II</b>·Rh,
effectively catalyzed Pauson–Khand cyclization reactions between
1,6-enynes and carbon monoxide at 10 times higher activity than the
homogeneous control. <b>II</b>·Rh was readily recovered
and used three times in Pauson–Khand cyclization reactions
without deterioration of yields or ee’s. Our work has expanded
the scope of MOF-catalyzed asymmetric reactions and showed that the
mixed linker strategy can effectively enlarge the open space around
the catalytic active site to accommodate highly sterically demanding
polycyclic metallocycle transition states/intermediates in asymmetric
intramolecular cyclization reactions