Abstract The organometallic approach is one of the most active topics in catalysis. application NH functionality catalysis has become an important and attractive concept catalyst design. moieties modifiers catalysts have been shown to various beneficial functions by molecular recognition through hydrogen bonding give catalyst–substrate, ligand–ligand, ligand–catalyst, catalyst–catalyst interactions. This Review summarizes recent progress development based on cooperative focusing moiety.

Two birds with one stone: the simultaneous production of two important bulk chemicals, methanol and ethylene glycol, from CO(2) oxide has been achieved under mild conditions by highly efficient homogeneous catalytic hydrogenation carbonate in presence a (PNP)Ru(II) catalyst.

Abstract A highly efficient catalyst system based on ruthenium‐pincer‐type complexes has been discovered for N‐formylation of various amines with CO 2 and H , thus affording the corresponding formamides excellent productivity (turnover numbers up to 1 940 000 in a single batch) selectivity. Using simple recycling protocol, was reused 12 runs N ‐dimethylformamide production without significant loss activity, demonstrating potential practical utilization this cost‐effective process. one‐pot...

From spiro to spiro: An iridium(I) complex with a spiral P,N ligand (SpinPhox) is highly efficient in the catalytic asymmetric hydrogenation of α,α′-bis(2-hydroxyarylidene) ketones afford corresponding aromatic spiroketals high yields excellent diastereo- and enantioselectivities (see scheme). The plays dual role reaction, acting as catalyst for both CC bonds subsequent spiroketalization bisphenolic ketones.

A series of MnI complexes containing lutidine-based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON=turnover number), broad substrate scope (81 examples), good functional-group tolerance, excellent enantioselectivities (85-98 % ee) in the hydrogenation various ketones. These aspects are rare earth-abundant metal catalyzed hydrogenations. utility protocol have demonstrated asymmetric synthesis...

From imines to amines through catalysis by Ir(I) complexes of a new type P,N ligand (see scheme): This reaction affords the corresponding optically active with up 98 % ee and has also been used perfect stereoselectivity in asymmetric synthesis sertraline (1), an important antidepressant chiral drug.

Showing a backbone: The spiroketal backbone of the bis(phosphine) ligand 1 led to good regio- and enantioselectivity in palladium-catalyzed asymmetric allylic amination racemic Morita–Baylis–Hillman adducts with aromatic amines. methodology provides facile efficient synthesis precursors for optically active β-lactam derivatives, including cholesterol drug Ezetimibe.

Copper–silica nanocomposite catalysts have been found to be highly efficient and stable in the heterogeneous hydrogenation of CO 2 -derived cyclic carbonates give methanol diols under relatively mild conditions.

An enantioselective alkoxycarbonylation-amination cascade process of terminal allenes with CO, methanol, and arylamines has been developed. It proceeds under mild conditions (room temperature, ambient pressure CO) via oxidative Pd(II) catalysis using an aromatic spiroketal-based diphosphine (SKP) as a chiral ligand Cu(II) salt oxidant affords wide range α-methylene-β-arylamino acid esters (36 examples) in good yields excellent enantioselectivity (up to 96% ee) high regioselectivity...

1,1′-Spirobiindane has been one type of privileged skeleton for chiral ligand design, and 1,1′-spirobiindane-based ligands have demonstrated outstanding performance in various asymmetric catalysis. However, the access to enantiopure spirobiindane is quite tedious, which obstructs its practical application. In present article, a facile enantioselective synthesis cyclohexyl-fused spirobiindanes accomplished, high yields excellent stereoselectivities (up >99% ee), via sequence Ir-catalyzed...

Abstract A Mn‐catalyzed diastereo‐ and enantioselective hydrogenation of α‐substituted β‐ketoamides has been realized for the first time under dynamic kinetic resolution conditions. anti ‐α‐Substituted β‐hydroxy amides, which are useful building blocks synthesis bioactive molecules chiral drugs, were prepared in high yields with excellent selectivity (up to >99 % dr ee ) unprecedentedly activity (TON up 10000). The origin stereoselectivity was clarified by DFT calculations.

ConspectusWhile spectacular successes have been achieved in homogeneous catalysis with the use of achiral diphosphine ligands featuring a wide natural bite angle, such as XantPhos, chiral diphosphines that can induce large P–M–P angle their transition metal complexes are conspicuously less explored asymmetric catalysis, probably due to challenges identification and efficient construction suitable backbone. In past decade, highly synthesis aromatic spiroketals corresponding (SKPs) has...

Zwei Fliegen mit einer Klappe: Die gleichzeitige Produktion der beiden wichtigen Grundchemikalien Methanol und Ethylenglycol ausgehend von CO2 Ethylenoxid gelingt unter milden Bedingungen über die hoch effiziente homogenkatalytische Hydrierung Ethylencarbonat in Gegenwart eines (PNP)RuII-Katalysators (siehe Schema). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available...

Abstract Optically active medium‐sized cyclic carbonyl compounds bearing an α‐chiral carbon center are of interest in pharmaceutical sciences and asymmetric synthesis. Herein, SpinPhox/Ir I catalysts have been demonstrated to be highly enantioselective the hydrogenation CC bonds exocyclic α,β‐unsaturated carbonyls, including a broad range α‐alkylidene lactams, unsaturated ketones, lactones. It is noteworthy that procedure can successfully used challenging α‐alkylidenelactam substrates with...

The enantioselective hydrogenation of a series challenging substrates, alpha-aryl-beta-substituted acrylic acids, was realized with high efficiency and enantioselectivity (up to 96%) under the catalysis Ir(i) complex Spiro-based P,N ligand, SpinPHOX.

Abstract A highly efficient catalyst system based on ruthenium‐pincer‐type complexes has been discovered for N‐formylation of various amines with CO 2 and H , thus affording the corresponding formamides excellent productivity (turnover numbers up to 1 940 000 in a single batch) selectivity. Using simple recycling protocol, was reused 12 runs N ‐dimethylformamide production without significant loss activity, demonstrating potential practical utilization this cost‐effective process. one‐pot...

Abstract Palladium‐catalyzed regio‐, diastereo‐, and enantioselective allylic alkylation of β‐ketocarbonyls with Morita–Baylis–Hillman adducts has been developed using a spiroketal‐based diphosphine (SKP) as the ligand, thus affording range densely functionalized products bearing vicinal tertiary all‐carbon quaternary stereodyad in high selectivities. The utility protocol was demonstrated by facile synthesis some complex molecules simple product transformations.

The Ir(I) complexes of chiral spiro phosphino–oxazoline ligands (SpinPhox) have demonstrated good to excellent enantioselectivity in the asymmetric hydrogenation (AH) a variety (E)-β,β-disubstituted α,β-unsaturated N-methoxy-N-methylamides, affording corresponding optically active Weinreb amides with up 97% ee.

Abstract Der metallorganische Ansatz ist eines der großen Themen auf dem Gebiet Katalyse, und insbesondere die Nutzung von NH‐Funktionen hat sich zu einem wichtigen attraktiven Konzept für das Katalysator‐Design entwickelt. NH‐Einheiten in metallorganischen Katalysatoren zeigen diverse positive Effekte vor allem durch molekulare Erkennung mittels Wasserstoffbrücken unter Ausbildung Katalysator‐Substrat‐, Ligand‐Ligand‐, Ligand‐ Katalysator‐ Katalysator‐Katalysator‐Wechselwirkungen. Dieser...

Abstract A palladium‐catalyzed asymmetric allyl–allyl cross‐coupling of acetates racemic Morita–Baylis–Hillman adducts and allylB(pin) has been developed using a spiroketal‐based bis(phosphine) as the chiral ligand, thus affording series 1,5‐dienes bearing vinylic ester functionality in good yields, high branched regioselectivities, uniformly excellent enantioselectivities (95–99 % ee). Further synthetic manipulations allylation products provided novel ways for rapid access to range...

A C2-symmetric chiral phosphine catalyst, NUSIOC-Phos, which can be easily derived from cyclohexyl-fused spirobiindane, was introduced. highly enantioselective domino process involving pyrrolidine-2,3-diones and γ-substituted allenoates catalyzed by NUSIOC-Phos has been disclosed. Diastereospecific tricyclic γ-lactams containing five contiguous stereogenic centers were obtained in high yields with nearly perfect enantioselectivities. kinetic resolution of racemic developed for the generation...

Abstract Von Iminen zu Aminen durch Katalyse mit Ir I ‐Komplexen eines neuartigen P,N‐Liganden (siehe Schema): Die Titelreaktion liefert die entsprechenden optisch aktiven Amine bis 98 % ee und ermöglichte perfekt stereoselektive Synthese von Sertralin ( 1 ), einem wichtigen Antidepressivum. magnified image

Von spiralig zu spiralig: Ein Iridium(I)-Komplex mit einem spiralen P,N-Liganden (SpinPhox) ist hoch effizient in der katalytischen asymmetrischen Hydrierung von α,α′-Bis(2-hydroxyaryliden)ketonen. Die entsprechenden aromatischen Spiroketale werden hohen Ausbeuten und exzellenten Diastereo- Enantioselektivitäten gebildet. Der Komplex hat eine Doppelrolle, indem er sowohl die CC-Bindungen als auch folgende Spiroketalisierung bisphenolischen Ketonen katalysiert.

An Ir/spiro[4,4]-1,6-nonadiene-based phosphine-oxazoline ligand (SpinPHOX) complex-catalyzed double asymmetric hydrogenation of 3,6-dialkylidene-1,4-dimethylpiperazine-2,5-diones has been developed, providing efficient and practical access to a wide variety chiral 3,6-disubstituted-2,5-diketopiperazines in high yields with exclusive cis-diastereo- excellent enantioselectivities (>99% de, up 98% ee). The synthetic utilities the protocol have demonstrated gram scale synthesis 6a construction...