Direct Stereospecific Amination of Alkyl and Aryl Pinacol Boronates

Mlynarski, Scott N.; Karns, Alexander S.; Morken, James P.

doi:10.1021/ja305448w

Cited by 229 publications

(154 citation statements)

References 33 publications

Supporting

Mentioning

151

Contrasting

Unclassified

Order By: Relevance

“…Attributing the lack of reactivity between the aminating agent and organoboron to their ineffective association, Morken and co-workers manipulated the nucleophilicity of methoxyamine by adding 3 equiv n BuLi to the reaction. [28] This enabled the lithiated methoxyamine to incorporate with pinacol boronate, forming an active “ate” complex which ultimately led to the primary amination product. The reaction proved to be efficient with electron-rich substrates, but electron-deficient ones generally resulted in low yields (Scheme 14).…”

Section: Carbon-nitrogen Bond Formationmentioning

confidence: 99%

Transition Metal‐Free ipso‐Functionalization of Arylboronic Acids and Derivatives

Zhu

Falck

2014

Adv Synth Catal

View full text Add to dashboard Cite

Arylboronic acids and their derivatives have been widely exploited as important synthetic precursors in organic synthesis, materials science, and pharmaceutical development. In addition to numerous applications in transition-metal-mediated cross-coupling reactions, transition-metal-free transformations involving arylboronic acids and derivatives have recently received a surge of attention for converting the C-B bond to C-C, C-N, C-O, and many other C-X bonds. Consequently, a wide range of useful compounds, e.g., phenols, anilines, nitroarenes, and haloarenes, have been readily synthesized. Amongst these efforts, many versatile reagents have been developed and a lot of practical approaches demonstrated. The research in this promising field is summarized in the current review and organized on the basis of the type of bonds being formed.

show abstract

Section: Carbon-nitrogen Bond Formationmentioning

confidence: 99%

Transition Metal‐Free ipso‐Functionalization of Arylboronic Acids and Derivatives

Zhu

Falck

2014

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…They could be purified by chromatography on silica gel and stored for several months in a freezer without any observable decomposition. The 1,4-hydroxyboronates are valuable intermediates that can be used in subsequent diastereoselective transformations, such as the conversion of the C-B bond into a C-N group to give 1,4-amino alcohols, 27 in the allylation of aldehydes and imines, 28 or in homologation reactions to give 1,5-diols. 29 Furthermore, we also carried out one-pot copper(I)-catalyzed addition-protection-oxidation sequences to give a series of orthogonally protected 1,4-diols 16, 19, 20 (Scheme 8; X = OH).…”

Section: Methodsmentioning

confidence: 99%

New Methods in Organic Synthesis Through Copper-Catalyzed Borylation Reactions: Stereoselective Synthesis of 1,4-Diols and Vinylboronates

Alfaro¹,

Parra²,

Alemán³

et al. 2013

Synlett

View full text Add to dashboard Cite

Boronic acid derivatives have become important intermediates in organic and medicinal chemistry and, as a result, the development of new methods that permit the efficient creation of C-B bonds under mild conditions has become an active field of research in organic synthesis. In the last ten years, copper-catalyzed borylation reactions have emerged as versatile new tools for introducing boron atoms into organic molecules. Here, we describe our recent research in this field. We have developed two coppercatalyzed borylation reactions. The first involves the S N 2′ addition of bis(pinacolato)diboron to allylic epoxides. This reaction permits the stereoselective synthesis of a wide range of compounds containing a 1,4-diol moiety, a fragment that is present in many natural products with important biological activities. The second reaction is a copper-catalyzed formal carboboration process. In this reaction, a C-B and a C-C bond are created in a single catalytic cycle, and the method provides a new tool for the synthesis of tri-and tetrasubstituted vinylboronates.

show abstract

“…More recently Morken has developed a mild amination protocol of pinacol boronic esters (Scheme 17) [41]. In this example the boronic ester was reacted with lithium methoxyamide to form an intermediate boronate complex 67 that rearranged to give the desired primary amines.…”

Section: Secondary Benzylic Carbamatesmentioning

confidence: 99%

Reagent-Controlled Lithiation–Borylation

Leonori

Aggarwal

2015

Synthesis and Application of Organoboron Compounds

View full text Add to dashboard Cite

Direct Stereospecific Amination of Alkyl and Aryl Pinacol Boronates

Abstract: The direct amination of alkyl and aryl pinacol boronates is accomplished with lithiated methoxyamine. This reaction directly provides aliphatic and aromatic amines, stereospecifically, and without preactivation of the boronate substrate.

Cited by 229 publications

References 33 publications

Transition Metal‐Free ipso‐Functionalization of Arylboronic Acids and Derivatives

Transition Metal‐Free ipso‐Functionalization of Arylboronic Acids and Derivatives

New Methods in Organic Synthesis Through Copper-Catalyzed Borylation Reactions: Stereoselective Synthesis of 1,4-Diols and Vinylboronates

Reagent-Controlled Lithiation–Borylation

Contact Info

Product

Resources

About