Rh(III)-Catalyzed Three-Component Syn-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

2021 ◽  
Author(s):  
Sumin Lee ◽  
Tomislav Rovis
Keyword(s):  
Amino Acid ◽  
Boronic Acid ◽  
Boronic Acids ◽  
Reductive Elimination ◽  
Amino Acid Derivatives ◽  
Arylboronic Acids ◽  
Migratory Insertion ◽  
Series Of Experiments ◽  
By Products ◽  
Aryl Boronic Acid

<p>Herein we report a Rh(III)-catalyzed three-component carboamination of alkenes from readily available aryl boronic acids as a carbon source and dioxazolones as nitrogen electrophiles. This protocol provides facile access to valuable amine products including <i>a</i>-amino acid derivatives in good yield and excellent regioselectivity without the need for a directing functionality. A series of experiments suggest a mechanism in which the Rh(III) catalyst undergoes transmetalation with the aryl boronic acid followed by turnover limiting, alkene migratory insertion into the Rh(III)-aryl bond. Subsequently, fast Rh-nitrene formation provides the <i>syn</i>-carboamination product selectively after reductive elimination and proto-demetalation. Importantly, the protocol provides 3-component coupling products in preference to a variety of 2-component undesired by-products.</p>

scholarly journals Rh(III)-Catalyzed Three-Component Syn-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

2021 ◽  
Author(s):  
Sumin Lee ◽  
Tomislav Rovis
Keyword(s):  
Amino Acid ◽  
Boronic Acid ◽  
Boronic Acids ◽  
Reductive Elimination ◽  
Amino Acid Derivatives ◽  
Arylboronic Acids ◽  
Migratory Insertion ◽  
Series Of Experiments ◽  
By Products ◽  
Aryl Boronic Acid

<p>Herein we report a Rh(III)-catalyzed three-component carboamination of alkenes from readily available aryl boronic acids as a carbon source and dioxazolones as nitrogen electrophiles. This protocol provides facile access to valuable amine products including <i>a</i>-amino acid derivatives in good yield and excellent regioselectivity without the need for a directing functionality. A series of experiments suggest a mechanism in which the Rh(III) catalyst undergoes transmetalation with the aryl boronic acid followed by turnover limiting, alkene migratory insertion into the Rh(III)-aryl bond. Subsequently, fast Rh-nitrene formation provides the <i>syn</i>-carboamination product selectively after reductive elimination and proto-demetalation. Importantly, the protocol provides 3-component coupling products in preference to a variety of 2-component undesired by-products.</p>

Highly enantioselective synthesis of α-tertiary chiral amino acid derivatives through rhodium-catalyzed asymmetric arylation of cyclic N-sulfonyl α-ketimino esters

2018 ◽  
Vol 16 (25) ◽  
pp. 4633-4640 ◽  
Author(s):  
Zheng Wang ◽  
Ming-Hua Xu
Keyword(s):  
Amino Acid ◽  
Enantioselective Synthesis ◽  
Amino Acid Derivatives ◽  
Arylboronic Acids

A simple sulfur-olefin ligand promoted Rh-catalyzed highly enantioselective arylation of cyclic α-ketimino esters with arylboronic acids is described.

scholarly journals Catabolism of Arylboronic Acids by Arthrobacter nicotinovorans Strain PBA

2003 ◽  
Vol 69 (7) ◽  
pp. 4263-4267 ◽  
Author(s):  
Ana C. Negrete-Raymond ◽  
Barbara Weder ◽  
Lawrence P. Wackett
Keyword(s):  
Carbon Atom ◽  
Oxygen Atom ◽  
Boronic Acid ◽  
Phenylboronic Acid ◽  
Boronic Acids ◽  
Ring Carbon ◽  
Arylboronic Acids ◽  
Arthrobacter Nicotinovorans ◽  
Ring Carbon Atom

ABSTRACT Arthrobacter sp. strain PBA metabolized phenylboronic acid to phenol. The oxygen atom in phenol was shown to be derived from the atmosphere using 18O2. 1-Naphthalene-, 2-naphthalene-, 3-cyanophenyl-, 2,5-fluorophenyl-, and 3-thiophene-boronic acids were also transformed to monooxygenated products. The oxygen atom in the product was bonded to the ring carbon atom originally bearing the boronic acid substituent with all the substrates tested.

scholarly journals Oxidative Hydroxylation of Aryl Boronic Acid Catalyzed by Co-porphyrin Complexes via Blue-Light Irradiation

Catalysts ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1262
Author(s):  
Alaa A. Atia ◽  
Masanari Kimura
Keyword(s):  
Blue Light ◽  
Biodegradable Polymers ◽  
Boronic Acid ◽  
Oxidation Process ◽  
Boronic Acids ◽  
Light Irradiation ◽  
Phenol Derivatives ◽  
Oxidative Reactions ◽  
Acid Catalyzed ◽  
Aryl Boronic Acid

Oxidative reactions often require unstable and environmentally harmful oxidants; therefore, the investigation of safer alternatives is urgent. Here, the hydroxylation of aryl boronic acid in the presence of Co-complexes is demonstrated. Tetrakis(4-carboxyphenyl) Co(II)-porphyrin was combined with biodegradable polymers such as chitosan catalyzed hydroxylation of phenyl boronic acids to form phenol derivatives under blue-light irradiation. This catalytic system can be used as an eco-friendly oxidation process that does not release oxidizing agents into the atmosphere.

scholarly journals Structural Requirements of 1-(2-Pyridinyl)-5-pyrazolones for Disproportionation of Boronic Acids

Molecules ◽  
2021 ◽  
Vol 26 (22) ◽  
pp. 6814
Author(s):  
Joungmo Cho ◽  
Venkata Subbaiah Sadu ◽  
Yohan Han ◽  
Yunsoo Bae ◽  
Hwajeong Lee ◽  
...  
Keyword(s):  
Boronic Acid ◽  
Boronic Acids ◽  
Bidentate Ligand ◽  
Arylboronic Acid ◽  
Structural Requirements ◽  
Arylboronic Acids ◽  
Pyrazolone Derivatives ◽  
Unusual Formation

We observed an unusual formation of four-coordinate boron(III) complexes from the reaction of 1-(2-pyridinyl)-5-pyrazolone derivatives with arylboronic acids in the basic media. The exact mechanism is not clear; however, the use of unprotected boronic acid and the presence of a bidentate ligand appeared to be the key structural requirements for the transformation. The results suggest that base-promoted disproportionation of arylboronic acid with the assistance of the [N,O]-bidentate ligation of 1-(2-pyridinyl)-5-pyrazolone should take place and facilitate the formation of pyrazole diarylborinate. Experiments to obtain a deeper understanding of its mechanism are currently underway.

ChemInform Abstract: Direct Amidation of Amino Acid Derivatives Catalyzed by Arylboronic Acids: Applications in Dipeptide Synthesis.

ChemInform ◽  
2014 ◽  
Vol 45 (6) ◽  
pp. no-no
Author(s):  
Shouxin Liu ◽  
Yihua Yang ◽  
Xinwei Liu ◽  
Farhana K. Ferdousi ◽  
Andrei S. Batsanov ◽  
...  
Keyword(s):  
Amino Acid ◽  
Amino Acid Derivatives ◽  
Arylboronic Acids ◽  
Direct Amidation

scholarly journals Synthesis of Boroxine and Dioxaborole Covalent Organic Frameworks via Transesterification and Metathesis of Pinacol Boronates

2021 ◽  
Author(s):  
Ehsan Hamzehpoor ◽  
Antranik Jonderian ◽  
eric mccalla ◽  
Dmitrii F. Perepichka
Keyword(s):  
Kinetic Analysis ◽  
Boronic Acid ◽  
Boronic Acids ◽  
Synthetic Approach ◽  
Covalent Organic Frameworks ◽  
Kinetic Measurements ◽  
H Nmr ◽  
Poorly Soluble ◽  
By Products ◽  
Model Reactions

Boroxine and dioxaborole are the first and some of the most studied synthons of Covalent Organic Frameworks (COFs). Despite their wide application in the design of functional COFs over the last 15 years, their synthesis still relies on the original Yaghi’s condensation of boronic acids (with itself or with polyfunctional catechols), some of which are difficult to prepare, poorly soluble, or unstable in the presence of water. Here we propose a new synthetic approach to boroxine COFs (based on transesterification of pinacol aryl boronates (ArBpin) with methyl boronic acid (MBA) and dioxaborole COFs (through the metathesis of pinacol boronates with methylboryl-protected catechols). The ArBpin and MBA-protected catechols are easy to purify, highly soluble, and bench-stable. Furthermore, kinetic analysis of the two model reactions reveals high reversibility (Keq~1) and facile control over the equilibrium. Unlike the conventional condensation which eliminates water by-products, the by-product of the metathesis (MBA pinacolate) allows for easy kinetic measurements of the COF formation by conventional <sup>1</sup>H NMR. We show the generality of this approach by synthesis of seven known boroxine/dioxaborole COFs whose crystallinity is better or equal to those reported by conventional condensation. We also apply metathesis polymerization to obtain two new COFs, Py4THB and B2HHTP, whose synthesis was previously precluded by their insolubility and hydrolytic instability, respectively, of the boronic acid precursors.<br>

scholarly journals Rhodium-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimines towards the synthesis of α,α-diaryl-α-amino acid derivatives

2015 ◽  
Vol 13 (17) ◽  
pp. 4918-4924 ◽  
Author(s):  
Ryosuke Takechi ◽  
Takahiro Nishimura
Keyword(s):  
Amino Acid ◽  
Ester Group ◽  
Amino Acid Derivatives ◽  
Asymmetric Addition ◽  
Arylboronic Acids ◽  
High Yields ◽  
Diene Complex

Rhodium/chiral diene complex-catalyzed asymmetric addition of arylboronic acids to cyclic ketimines having an ester group proceeded to give the corresponding α-amino acid derivatives in high yields with high enantioselectivity.

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