The new world of organic reactions in water

2013 ◽  
Vol 85 (6) ◽  
pp. 1089-1101 ◽  
Author(s):  
Shū Kobayashi
Keyword(s):  
Organic Solvents ◽  
New World ◽  
Aqueous Ammonia ◽  
Aqueous Media ◽  
Organic Reactions ◽  
Primary Amines ◽  
Allylic Amination ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
High Yields

Different reactivities and selectivities are observed in water compared with those in organic solvents. In this article, such three examples are described. While ammonia was known not to react in metal-catalyzed allylic amination, palladium-catalyzed allylic amination using aqueous ammonia proceeded to afford primary amines in high yields. Second, allylboronates reacted with aldehydes in aqueous media to afford α-addition adducts exclusively in high yields with high diastereo- and enantioselectivities using Zn(OH)2with ligands as catalysts. Finally, it was found that catalytic use of In(0) was effective for the reactions of allylboronates with ketones in water.

Palladium-catalyzed amination of allylic carbonates with ammonia: access to primary amines

2014 ◽  
Vol 1 (11) ◽  
pp. 1266-1269 ◽  
Author(s):  
Peng Yin ◽  
Mun Yee Wong ◽  
Jieying Tham ◽  
Teck-Peng Loh
Keyword(s):  
Aqueous Ammonia ◽  
Primary Amines ◽  
Allylic Amination ◽  
Ammonia Gas ◽  
Palladium Catalyzed

Allylic amination of allylic carbonates with ammonia gas or aqueous ammonia was successfully carried out using (SIPr)Pd(allyl)Cl as the catalyst and Ph3P, which is essential for the reaction.

scholarly journals Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Ye-Wei Chen ◽  
Yang Liu ◽  
Han-Yu Lu ◽  
Guo-Qiang Lin ◽  
Zhi-Tao He
Keyword(s):  
Organic Synthesis ◽  
Allylic Substitution ◽  
Palladium Hydride ◽  
Substitution Process ◽  
Wide Range ◽  
Leaving Group ◽  
Palladium Catalyzed ◽  
Potential Factors ◽  
Metal Catalyzed ◽  
High Yields

AbstractTransition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp3)-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp3)-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pKa values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process.

Palladium-catalyzed asymmetric allylic amination of racemic butadiene monoxide with isatin derivatives

2015 ◽  
Vol 13 (20) ◽  
pp. 5826-5830 ◽  
Author(s):  
Gen Li ◽  
Xiangqing Feng ◽  
Haifeng Du
Keyword(s):  
Allylic Amination ◽  
Palladium Catalyzed ◽  
High Yields ◽  
Isatin Derivatives

Pd-catalyzed asymmetric aminations of butadiene monoxide with isatin derivatives using P/alkene ligands gave high yields, ees and regioselectivity ratios.

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