Catalytic Enantioselective Boryl and Silyl Substitution with Trifluoromethyl Alkenes: Scope, Utility, and Mechanistic Nuances of Cu–F β-Elimination DOI
Paulo H. S. Paioti, Juan del Pozo,

Malte S. Mikus

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(50), P. 19917 - 19934

Published: Dec. 6, 2019

Catalytic enantioselective methods are introduced that allow access to a variety of allyl boronates and silanes contain difluoroalkene unit; the resulting products may be used for preparation organofluorine compounds in high enantiomeric purity. Furthermore, number key mechanistic aspects transformations have been investigated analyzed. Thus, first, an NHC–Cu-catalyzed method boryl substitution with F3C-substituted alkenes is introduced. These processes, unlike previously reported strategies, applicable alkyl as well aryl substituted substrates, afford bearing moiety (up 98% yield 95:5 er). Second, corresponding silyl substitutions, first cases their kind, presented 94% 97:3 Third, experimental computational (DFT) investigations described shed light on catalytic processes. Evidence (X-ray structures Cu–alkyl intermediates kinetic studies) put forth illustrating initial Cu–boryl Cu–silyl addition significantly faster than ensuing Cu–F elimination, latter step can facilitated by either mild Lewis acid (e.g., Li or Na cation) nucleophilic promoter alkoxide). findings together DFT studies demonstrate β-elimination probably proceeds anti-stereochemistry. Representative ways through which new understanding rationalize disclosed findings, improve transformation, develop diastereo- provided. For example, explanation provided regarding why bisphosphine–Cu complexes do not efficiently promote substitutions aryl-substituted but facile, how size ligand impact regioselectivity efficiency.

Language: Английский

Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre DOI
Jaehee Lee, Suttipol Radomkit, Sebastian Torker

et al.

Nature Chemistry, Journal Year: 2017, Volume and Issue: 10(1), P. 99 - 108

Published: Oct. 2, 2017

Language: Английский

Citations

135
Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides DOI
Yuan Huang,

Kevin B. Smith,

M. Kevin Brown

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(43), P. 13314 - 13318

Published: Aug. 29, 2017

A method for the copper-catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration alkene, followed by capture generated alkyl-copper intermediate with an acid chloride. reactions operated low catalyst loading and generally occurre within 15 min at room temperature a range alkenes. In case vinyl arenes, enantioselective was possible.

Language: Английский

Citations

128
Diastereodivergent Synthesis of β‐Amino Alcohols by Dual‐Metal‐Catalyzed Coupling of Alkoxyallenes with Aldimine Esters DOI
Minghui Zhu, Qinglong Zhang, Weiwei Zi

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(12), P. 6545 - 6552

Published: Dec. 4, 2020

Abstract Both syn ‐ and anti ‐β‐amino alcohols are common structural motifs in natural products, drug molecules, chiral ligands catalysts. However, the currently available methods for synthesizing these limited to generate only one diastereoisomer. Therefore, development of a unified method stereoselective access complementary diastereomers would be highly desirable. Herein, we report dual‐metal‐catalyzed diastereodivergent coupling alkoxyallenes with aldimine esters. By carefully selecting two metals appropriate ligands, could synthesize both alcohol high enantioselectivity diastereoselectivity from same set starting materials. Furthermore, stereodivergent syntheses all four stereoisomers β‐amino achieved. We demonstrated synthetic utility this by concisely mycestericins F G.

Language: Английский

Citations

128
Migratory Arylboration of Unactivated Alkenes Enabled by Nickel Catalysis DOI
Wang Wang, Chao Ding, Yangyang Li

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(14), P. 4612 - 4616

Published: Feb. 11, 2019

Abstract An unprecedented arylboration of unactivated terminal alkenes, featuring 1, n ‐regioselectivity, has been achieved by nickel catalysis. The nitrogen‐based ligand plays an essential role in the success this three‐component reaction. This transformation displays good regioselectivity and excellent functional‐group tolerance. In addition, incorporation a boron group into products provides substantial opportunities for further transformations. Also demonstrated is that can be readily transformed pharmaceutically relevant molecules. Unexpectedly, preliminary mechanistic studies indicate although metal migration favors α‐position boron, selective decisive bond formation favored at benzylic position.

Language: Английский

Citations

127
Catalytic Enantioselective Boryl and Silyl Substitution with Trifluoromethyl Alkenes: Scope, Utility, and Mechanistic Nuances of Cu–F β-Elimination DOI
Paulo H. S. Paioti, Juan del Pozo,

Malte S. Mikus

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(50), P. 19917 - 19934

Published: Dec. 6, 2019

Catalytic enantioselective methods are introduced that allow access to a variety of allyl boronates and silanes contain difluoroalkene unit; the resulting products may be used for preparation organofluorine compounds in high enantiomeric purity. Furthermore, number key mechanistic aspects transformations have been investigated analyzed. Thus, first, an NHC–Cu-catalyzed method boryl substitution with F3C-substituted alkenes is introduced. These processes, unlike previously reported strategies, applicable alkyl as well aryl substituted substrates, afford bearing moiety (up 98% yield 95:5 er). Second, corresponding silyl substitutions, first cases their kind, presented 94% 97:3 Third, experimental computational (DFT) investigations described shed light on catalytic processes. Evidence (X-ray structures Cu–alkyl intermediates kinetic studies) put forth illustrating initial Cu–boryl Cu–silyl addition significantly faster than ensuing Cu–F elimination, latter step can facilitated by either mild Lewis acid (e.g., Li or Na cation) nucleophilic promoter alkoxide). findings together DFT studies demonstrate β-elimination probably proceeds anti-stereochemistry. Representative ways through which new understanding rationalize disclosed findings, improve transformation, develop diastereo- provided. For example, explanation provided regarding why bisphosphine–Cu complexes do not efficiently promote substitutions aryl-substituted but facile, how size ligand impact regioselectivity efficiency.

Language: Английский

Citations

119