Lithium Amino Alkoxide-Evans Enolate Mixed Aggregates: Aldol Addition with Matched and Mismatched Stereocontrol.

Title Lithium Amino Alkoxide-Evans Enolate Mixed Aggregates: Aldol Addition with Matched and Mismatched Stereocontrol.
Authors J. Jermaks; E.H. Tallmadge; I. Keresztes; D.B. Collum
Journal J Am Chem Soc
DOI 10.1021/jacs.7b13776
Abstract

Building on structural and mechanistic studies of lithiated enolates derived from acylated oxazolidinones (Evans enolates) and chiral lithiated amino alkoxides, we found that amino alkoxides amplify the enantioselectivity of aldol additions. The pairing of enantiomeric series affords matched and mismatched stereoselectivities. The structures of mixed tetramers showing 2:2 and 3:1 (alkoxide-rich) stoichiometries are determined spectroscopically. Rate and computational studies provide a viable mechanistic and stereochemical model based on the direct reaction of the 3:1 mixed tetramers, but they raise unanswered questions for the 2:2 mixed aggregates.

Citation J. Jermaks; E.H. Tallmadge; I. Keresztes; D.B. Collum.Lithium Amino Alkoxide-Evans Enolate Mixed Aggregates: Aldol Addition with Matched and Mismatched Stereocontrol.. J Am Chem Soc. 2018;140(8):30773090. doi:10.1021/jacs.7b13776

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Lithium

Lithium Bohr ModelSee more Lithium products. Lithium (atomic symbol: Li, atomic number: 3) is a Block S, Group 1, Period 2 element with an atomic weight of 6.94. The number of electrons in each of Lithium's shells is [2, 1] and its electron configuration is [He] 2s1. The lithium atom has a radius of 152 pm and a Van der Waals radius of 181 pm. Lithium was discovered by Johann Arvedson in 1817 and first isolated by William Thomas Brande in 1821. The origin of the name Lithium comes from the Greek wordlithose which means "stone." Lithium is a member of the alkali group of metals. It has the highest specific heat and electrochemical potential of any element on the period table and the lowest density of any elements that are solid at room temperature. Elemental LithiumCompared to other metals, it has one of the lowest boiling points. In its elemental form, lithium is soft enough to cut with a knife its silvery white appearance quickly darkens when exposed to air. Because of its high reactivity, elemental lithium does not occur in nature. Lithium is the key component of lithium-ion battery technology, which is becoming increasingly more prevalent in electronics.

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