Recent Advances in Asymmetric Catalysis Using p‐Block Elements DOI Creative Commons
Milan Pramanik, Michael G. Guerzoni, Emma Richards

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(9)

Published: Dec. 1, 2023

Abstract The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone organic synthesis. Typically, metal catalysts bearing chiral ligands as well organocatalysts have been employed the synthesis compounds. In this review, we highlight recent advances in main group catalysis using p‐block elements (boron, aluminium, phosphorus, bismuth) complementary and sustainable approach to molecules. Several these benefit terms high abundance, low toxicity, selectivity, excellent reactivity. This minireview summarises utilisation element asymmetric value‐added

Language: Английский

Incorporation of Chiral Frustrated Lewis Pair into Metal–Organic Framework with Tailored Microenvironment for Heterogeneous Enantio- and Chemoselective Hydrogenation DOI Creative Commons
Yin Zhang, Yao Jiang, Ayman Nafady

et al.

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(8), P. 1692 - 1701

Published: July 27, 2023

The development of efficient heterogeneous catalysts with multiselectivity (e.g., enantio- and chemoselectivity) has long been sought after but limited progress being made so far. To achieve chemoselectivity in a system, as inspired by enzymes, we illustrate herein an approach creating enzyme-mimic region (EMR) within the nanospace metal–organic framework (MOF) exemplified context incorporating chiral frustrated Lewis pair (CFLP) into MOF tailored pore environment. Due to high density EMR featuring active site CFLP auxiliary sites hydroxyl group/open metal vicinity CFLP, resultant EMR@MOF demonstrated excellent catalysis performance hydrogenation α,β-unsaturated imines afford β-unsaturated amines yields chemoselectivity. role regulating was proved observation catalyst–substrate interaction experimentally, which also rationalized computational results. This work not only contributes new platform for multiselective opens promising avenue develop challenging yet important transformations.

Language: Английский

Citations

18
Recent Advances in Asymmetric Catalysis Using p‐Block Elements DOI Creative Commons
Milan Pramanik, Michael G. Guerzoni, Emma Richards

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(9)

Published: Dec. 1, 2023

The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone organic synthesis. Typically, metal catalysts bearing chiral ligands as well organocatalysts have been employed the synthesis compounds. In this review, we highlight recent advances in main group catalysis using p-block elements (boron, aluminium, phosphorus, bismuth) complementary and sustainable approach to molecules. Several these benefit terms high abundance, low toxicity, selectivity, excellent reactivity. This minireview summarises utilisation element asymmetric value-added

Language: Английский

Citations

11
Borane‐Catalyzed Asymmetric Reduction of 2‐Alkylpyridines† DOI Open Access
Heng Luo,

Zhao‐Ying Yang,

Ming Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(23), P. 3088 - 3092

Published: Aug. 8, 2024

Comprehensive Summary Herein, a method for the enantioselective reduction of unprotected 2‐alkylpyridines is reported first time. By using pinacolborane and an amide as reducing agents, large number 2‐alkylpiperidines were synthesized with high yields excellent enantioselectivities via cascade process involving 1,4‐hydroboration subsequent transfer hydrogenation. The resulting products can be easily converted to natural alkaloids.

Language: Английский

Citations

2
An un-forgotten classic: the nitro-Mannich reaction between nitrones and silyl nitronates catalysed by B(C6F5)3 DOI Creative Commons
Michael G. Guerzoni, Yara van Ingen, Rasool Babaahmadi

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(7), P. 2648 - 2654

Published: Jan. 1, 2024

Herein we report the B(C 6 F 5 ) 3 -catalysed nitro-Mannich reaction between nitrones and silyl nitronates, affording silyl-protected α-nitro hydroxylamines with yields up to 99% diastereoselectivities 99 : 1.

Language: Английский

Citations

2
Stereocontrol via Propeller Chirality in FLP‐Catalyzed Asymmetric Hydrogenation DOI Creative Commons

Bianka Kótai,

Gábor Laczkó,

Andrea Hamza

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(21)

Published: Jan. 31, 2024

Abstract Utilization of chiral frustrated Lewis pairs as catalysts in enantioselective hydrogenation unsaturated molecules represents a promising approach asymmetric synthesis. In our effort to improve current understanding the factors governing stereoselectivity these catalytic processes, herein we examined mechanism direct aromatic enamines catalyzed by binaphthyl–based amino–borane. Our computational analysis reveals that only one particular conformer key borohydride reaction intermediate can be regarded reactive form this species. This has well–defined propeller shape, which induces facial selectivity hydride transfer pro–chiral iminium intermediates. The chirality is generated axially binaphthyl scaffold amino–borane catalyst through stabilizing π‐π stacking interactions. new insight readily used interpret high degree stereoinduction observed for reactions. We expect concept relay could further exploited design endeavors.

Language: Английский

Citations

2
Regulating iminophosphorane PN bond reactivity through geometric constraints with cage-shaped triarylphosphines DOI Creative Commons
Lei Hu,

Sayandip Chakraborty,

Nikolay Tumanov

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(55), P. 7073 - 7076

Published: Jan. 1, 2024

Structure-reactivity investigations and quantum-chemical parametrization of steric electronic properties geometrically constrained iminophosphoranes enabled the design new frustrated Lewis pairs revealed unusual at phosphonium center embedded in cage-shaped triptycene tricyclic scaffold.

Language: Английский

Citations

1
IUPAC’s 2024 Top Ten Emerging Technologies in Chemistry DOI
Fernando Gomollón‐Bel

Chemistry International, Journal Year: 2024, Volume and Issue: 46(4), P. 8 - 16

Published: Oct. 1, 2024

Abstract In 2019, the IUPAC started a quest to select most interesting emerging technologies in chemical sciences [1]. Now, this established initiative continues year after year—adding ideas list of innovations with an enormous potential transform fields as diverse materials science, energy, healthcare, agriculture and computing, among others [2]. Overall, “Top Ten Emerging Technologies Chemistry” align United Nations’ Sustainable Development Goals, secure sustainable future pave way circular economy [3]. This new delves into materials, unexplored physical phenomena, creative solutions global challenges, including prevalent diseases still ongoing energy fuel crisis. As first Ten” paper, hover over broad range readiness—from laboratory discoveries commercial realities, hence “emerging.” But all them, carefully curated by panel experts nominated IUPAC, are equally exciting. Read on.

Language: Английский

Citations

1
Asymmetric catalysis by chiral FLPs: A computational mini‐review DOI
Shanti G. Patra

Chirality, Journal Year: 2024, Volume and Issue: 36(5)

Published: April 25, 2024

Steric hindrance in Lewis acid (LA) and base (LB) obstruct the acid-base adduct formation, pair was termed as frustrated (FLP). In past 16 years, field of enantioselective catalysis by chiral FLPs has been slowly growing. It shown that LAs are significant they involved hydrogen transfer (HT) step to imine, resulting enantioselectivity. After H

Language: Английский

Citations

0
Understanding the enhanced reactivity of strained intramolecular Frustrated Lewis Pairs DOI Creative Commons
Susana Portela, Israel Fernández

Zeitschrift für anorganische und allgemeine Chemie, Journal Year: 2023, Volume and Issue: 649(6-7)

Published: Jan. 12, 2023

Abstract The poorly understood factors controlling the enhanced reactivity of strained intramolecular frustrated Lewis pairs (FLPs) having a rigid biphenylene tether have been quantitatively explored in detail by means computational methods. With help activation strain model and energy decomposition analysis methods, challenging allene reaction has selected compared to analogous process mediated related FLP more flexible tether, which is significantly less reactive. In addition, influence nature acid atom on considered as well showing that steadily decreases when going down group 13.

Language: Английский

Citations

0
Recent Advances in Asymmetric Catalysis Using p‐Block Elements DOI Creative Commons
Milan Pramanik, Michael G. Guerzoni, Emma Richards

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(9)

Published: Dec. 1, 2023

Abstract The development of new methods for enantioselective reactions that generate stereogenic centres within molecules are a cornerstone organic synthesis. Typically, metal catalysts bearing chiral ligands as well organocatalysts have been employed the synthesis compounds. In this review, we highlight recent advances in main group catalysis using p‐block elements (boron, aluminium, phosphorus, bismuth) complementary and sustainable approach to molecules. Several these benefit terms high abundance, low toxicity, selectivity, excellent reactivity. This minireview summarises utilisation element asymmetric value‐added

Language: Английский

Citations

0