2021
DOI: 10.1002/anie.202100643
|View full text |Cite
|
Sign up to set email alerts
|

Amino Acid‐Functionalized Metal‐Organic Frameworks for Asymmetric Base–Metal Catalysis

Abstract: We report a strategy to develop heterogeneous single‐site enantioselective catalysts based on naturally occurring amino acids and earth‐abundant metals for eco‐friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal‐organic framework (MOF), followed by post‐synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF‐Fe catalyst displayed… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
5

Citation Types

0
49
0

Year Published

2021
2021
2024
2024

Publication Types

Select...
9

Relationship

2
7

Authors

Journals

citations
Cited by 70 publications
(49 citation statements)
references
References 108 publications
0
49
0
Order By: Relevance
“…In the field of hydroboration, the context is even more unexplored. The synthesis of alcohols through this route has been explored via MOF systems based on Ti, Fe, Co, and Mg [25][26][27][28][29][30]; however, there are no precedents with these supramolecular entities built on lanthanides precursors. Therefore, in this work, the first example of yttrium and europiumbased mixed MOF, with the formula {[Y 3.5 Eu 1.5 L 6 (OH) 3 (H 2 O) 3 ]•12DMF} n , is presented, taking the strong background of our group in the examination of these supramolecular systems in catalysis [15,16].…”
Section: Introductionmentioning
confidence: 99%
“…In the field of hydroboration, the context is even more unexplored. The synthesis of alcohols through this route has been explored via MOF systems based on Ti, Fe, Co, and Mg [25][26][27][28][29][30]; however, there are no precedents with these supramolecular entities built on lanthanides precursors. Therefore, in this work, the first example of yttrium and europiumbased mixed MOF, with the formula {[Y 3.5 Eu 1.5 L 6 (OH) 3 (H 2 O) 3 ]•12DMF} n , is presented, taking the strong background of our group in the examination of these supramolecular systems in catalysis [15,16].…”
Section: Introductionmentioning
confidence: 99%
“…It is relatively difficult to insert and modify functional groups in the structures of conventional porous solids such as zeolites and activated carbons, especially at the molecular level, whereas metal-organic frameworks (MOFs), newly developed porous crystalline materials constructed by metal clusters and organic linkers, are acknowledged to be relatively easy in this regard [5][6][7][8][9] . Because of their highly diversified structure, tailorable porosity, and tunable functionality, MOFs show great potential in various areas including adsorption [10][11][12] , catalysis [13,14] , chemical sensing [15,16] , and electrochemistry [17,18] . Endowed with these fantastic features, MOFs are an ideal platform to customize functional materials on demand.…”
Section: Introductionmentioning
confidence: 99%
“…Chiral 1,2-amino alcohols are versatile structural motifs widely present in biologically active molecules. Although chiral 1,2-amino alcohols are easily affordable by reducing naturally occurring amino acids, their application as chiral bidentate ligands in base-metal catalysis is very limited, presumably due to the absence of sterically bulky substituents that leads to the formation of oligomeric metal species or intermolecular decomposition. In asymmetric catalysis, amino acid-derived 1,2-amino alcohols have been primarily employed as chiral auxiliaries or the source of a stereogenic center in the ligand component of the base-metal catalysts, or ligands after multistep derivatization. ,, Grafting of amino alcohols onto porous solid supports followed by metalation could provide robust single-site earth-abundant metal catalysts that would impose excellent chiral induction within pores for enantioselective catalysis. As a porous and tunable molecular material, metal–organic frameworks (MOFs) have emerged as an interesting class of supports to prepare heterogeneous and robust chiral base-metal catalysts via active-site isolation. Owing to their modular and tunable properties, the chemoselectivity and enantioselectivity of chiral MOF-catalysts could be easily optimized by adjusting pore sizes and postsynthetic modification techniques. ,, In addition, the precise knowledge of crystalline MOF structures by X-ray crystallography provides distinct advantages over other supported chiral catalysts by enabling rational tuning of catalytic activities/selectivities through the use of tailor-made building blocks and direct observation of structure–activity relationships.…”
Section: Introductionmentioning
confidence: 99%
“…37−72 Owing to their modular and tunable properties, the chemoselectivity and enantioselectivity of chiral MOF-catalysts could be easily optimized by adjusting pore sizes and postsynthetic modification techniques. 42,73,74 In addition, the precise knowledge of crystalline MOF structures by X-ray crystallography provides distinct advantages over other supported chiral catalysts by enabling rational tuning of catalytic activities/ selectivities through the use of tailor-made building blocks and direct observation of structure−activity relationships.…”
Section: ■ Introductionmentioning
confidence: 99%