A new type of L-Tertiary leucine-derived ligand: Synthesis and application in Cu(II)-catalyzed asymmetric Henry reactions

Cai, Zedong; Lan, Ting; Ma, Pengfei; Zhang, Jingfang; Yang, Qing‐Qing; He, Wei

doi:10.1016/j.tet.2019.130469

Cited by 2 publications

(1 citation statement)

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“…Despite its theoretical potential to deliver fully substituted [ N ]-asymmetric centers, the majority of extant Henry examples focus on utilizing nitromethane as the nucleophilic partner (Scheme a, scenario 1). − As the complexity of the nitroalkane pronucleophile increases, issues around undesired reactivity compromise the efficiency and practicality of the reactions. − , Careful control of the basicity of the reaction medium is necessary in order to suppress undesired condensation products (Scheme a, scenarios 1–2) and product decomposition through retro-aldol reactions. − The latter is aggravated for scenarios 3–4, presented in Scheme a, wherein the steric profile of bulky alkyl substituents favor bond breakage. To circumvent these issues, extant methods often require reactions to be performed at cryogenic temperatures and employ transition metal catalysts to achieve high levels of stereocontrol.…”

Section: Introductionmentioning

confidence: 99%

Crystallization-Enabled Henry Reactions: Stereoconvergent Construction of Fully Substituted [N]-Asymmetric Centers

Cruz

Johnson

2022

J. Am. Chem. Soc.

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Tetrasubstituted stereogenic carbon centers bearing a nitrogen substituent represent important motifs in medicinal chemistry and natural products; therefore, the development of efficient methods for the stereoselective synthesis of this class of compounds continues to be an important problem. This article describes stereoconvergent Henry reactions of γ,γ-disubstituted nitroalkanes to deliver highly functionalized building blocks containing up to five contiguous stereogenic centers including a fully substituted [N]-asymmetric center. Henry reactions of higher order nitroalkanes are often characterized by their reversibility and minimal accompanying thermodynamic stereocontrol. In contrast, mechanistic studies for the present case suggest a scenario in which reversibility is productively leveraged through crystallizationbased stereocontrol, thereby enabling the efficient sequential π-additions of readily accessible starting materials to assemble complex acyclic stereoarrays.

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