Abstract
This Account describes our research over the past decade in the
asymmetric alkyne addition to aldehydes to generate optically active
propargylic alcohols. Our methods employ a dialkylzinc reagent to
react with a terminal alkyne to form an alkynylzinc nucleophile,
and can be grouped into the BINOL-catalyzed reactions and the functionalized
BINOL catalyzed reactions. We first describe the development of
the BINOL-ZnEt2 -Ti(Oi -Pr)4 catalyst
system, and its modification through the use of Lewis base additives
to form the alkynylzinc at room temperature. The substrate scope
compatible with these methods and the enantioselectivities achieved
are discussed. We then describe the functionalized BINOL and H8 BINOL catalyst
systems, which can be further divided into classes based on the
manner in which the BINOL framework has been modified. Generally,
these functionalized BINOL and H8 BINOL derivatives contain
internal Lewis basic sites which can both promote the formation
of the nucleophilic alkynylzinc reagents at reduced temperature
and modify the catalytic properties of the chiral biaryl unit. In a
few cases, these catalysts also show good efficiency even without the
use of the Ti(IV) reagent. The catalytic methods in this Account have
demonstrated that a wide range of alkyne and aldehyde substrates
can be subjected to the asymmetric addition reactions to generate
structurally diverse chiral propargylic alcohols with high enantioselectivity.
Some of these methods have exhibited high practicality in synthesis.
1 Introduction
2 BINOL-Based Catalytic Systems
2.1 Catalysis by BINOL-ZnEt2 -Ti(Oi -Pr)4
2.2 Catalysis by BINOL-ZnEt2 -Ti(Oi -Pr)4 -HMPA
2.3 Catalysis by BINOL-ZnEt2 -Ti(Oi -Pr)4 -NMI
2.4 Catalysis by BINOL-ZnEt2 -Ti(Oi- Pr)4 -Cy2 NH
3 Functionalized BINOL-Based Catalytic Systems
3.1 Catalysis by 3,3′-Dianisyl-BINOLs and -H8 BINOLs
3.2 Catalysis by 3,3′-Bis(diphenylmethoxy)methyl Substituted BINOLs
3.3 Catalysis by Acyclic and Macrocyclic Binaphthyl Salens
3.4 Catalysis by 3,3′-Bismorpholinomethyl H8 BINOL
3.5 Catalysis by C
1 -Symmetric
BINOL-Terpyridine
4 Summary
Key words
alkyne addition to aldehydes - BINOL-based catalytic systems -
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