Pd-catalyzed asymmetric allylic substitution reactions using P-chirogenic diaminophosphine oxides: DIAPHOXs

This paper describes the development of a new class of chiral phosphorus ligand: aspartic acid-derived P-chirogenic diaminophosphine oxides, DIAPHOXs, and their application to several Pd-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation was initially examined in detail using diaminophosphine oxides 1a, resulting in the highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 12, which functions as the actual ligand. Furthermore, asymmetric allylic amination was examined using Pd-DIAPHOX catalyst systems, providing a variety of chiral allylic amines.     

Pd-catalyzed asymmetric allylic amination using aspartic acid derived P-chirogenic diaminophosphine oxides: DIAPHOXs

[reaction: see text] A Pd-catalyzed asymmetric allylic amination using aspartic acid derived P-chirogenic diaminophosphine oxides (DIAPHOXs) is described. Asymmetric allylic amination of both linear and cyclic substrates proceeded at room temperature to give the chiral allylic amines in 72-99% ee.     

Pd-catalyzed asymmetric allylic amination of Morita-Baylis-Hillman adduct derivatives using chiral diaminophosphine oxides: DIAPHOXs

[reaction: see text] Asymmetric allylic amination of allylic carbonates prepared from racemic Morita-Baylis-Hillman adducts proceeded in the presence of Pd catalyst, chiral diaminophosphine oxide (DIAPHOX), and BSA, affording the corresponding chiral aza-Morita-Baylis-Hillman adduct derivatives in excellent yield with up to 99% ee. The cyclic reaction products could be converted into various synthetically useful compounds such as chiral cyclic beta-amino acids.     

Ir-catalyzed asymmetric allylic amination using chiral diaminophosphine oxides

An Ir-catalyzed asymmetric allylic amination using chiral diaminophosphine oxide is described. Asymmetric allylic amination of terminal allylic carbonates proceeded in the presence of 2 mol % of Ir catalyst, 2 mol % of chiral diaminophosphine oxide, 5 mol % of NaPF₆, and BSA, affording the chiral branched allylic amines in up to 95% ee.     

Ir-catalyzed asymmetric allylic alkylation using chiral diaminophosphine oxides: DIAPHOXs. Formal enantioselective synthesis of (−)-paroxetine

An Ir-catalyzed asymmetric allylic alkylation using chiral diaminophosphine oxide is described. Asymmetric allylic alkylation of terminal allylic carbonates proceeded using 5 mol % of Ir catalyst, 5 mol % of DIAPHOX 1i, 10 mol % of NaPF₆, 10 mol % of LiOAc, and N,O-bis(trimethylsilyl)acetamide (BSA), affording the corresponding branched products in excellent yield and in up to 95% ee. The developed catalytic asymmetric reaction was successfully applied to a formal enantioselective synthesis of (−)-paroxetine.     

过渡金属催化高选择性膦氢化反应

本文总结了过去几十年特别是近15年来过渡金属催化下各种含磷-氢键的膦氢化合物对炔烃的高选择性膦氢化反应,详尽叙述了其发现、发展和现状.自1996年来,过渡金属催化高选择性膦氢化反应研究工作发展迅速,各种高选择性膦氢化反应不断开发,目前已具有底物适用范围广、过渡金属催化剂活性高、反应选择性高、原子经济性高、以及能满足不同合成需求等优点,并逐步向反应条件温和化、金属催化剂简单化、无配体化、合成步骤简易化以及原料催化剂成本低价化方向发展.虽然如此,至今仍缺乏关于本研究全面的综述和介绍,希望本文可以弥补文献缺陷,对过渡金属催化高选择性膦氢化反应研究有个客观全面的介绍.过渡金属催化烯烃的不对称膦氢化反应合成碳手性或磷手性的光学活性有机磷化合物作为相关研究中的起步最晚的分支,本文也将作阶段小结.     

Development of a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. A unique source of enantioselection in Pd-catalyzed asymmetric construction of quaternary carbons

[reaction: see text] We have recently developed a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. These pentavalent phosphorus compounds have been successfully applied to Pd-catalyzed asymmetric construction of tertiary and quaternary carbons. The actual ligand structure was the trivalent phosphorus species 17, which was generated in situ by BSA-induced P(V) to P(III) transformation of 6, the preligand. Detailed mechanistic studies, including asymmetric amplification and initial rate kinetics, revealed that complex 18 [Pd-17 (1:2) complex] was the active catalyst. The important function of the nitrogen atom on the sidearm in the ligands was also clarified. The source of enantioselection in the construction of asymmetric quaternary carbons was the secondary ligand substrate interaction mediated by N-Zn coordination.     

超临界二氧化碳介质中的过渡金属催化反应

主要综述了以超临界二氧化碳作为反应介质的过渡金属催化加氢、羰基化、Heck和Stille反应的最新研究进展。     

Transition metal-catalyzed organic reactions in undivided electrochemical cells

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation. This conversion mainly focuses on transition metal-catalyzed anodic oxidation and cathodic reduction and great progress has been achieved in both areas. Typically, only one of the half-cell reactions is involved in the organic reaction while a sacrificial reaction occurs at the counter electrode, which is inherently wasteful since one electrode is not being used productively. Recently, transition metal-catalyzed paired electrolysis that makes use of both anodic oxidation and cathodic reduction has attracted much attention. This perspective highlights the recent progress of each type of electrochemical reaction and relatively focuses on the transition metal-catalyzed paired electrolysis, showcasing that electrochemical reactions involving transition metal catalysis have advantages over conventional reactions in terms of controlling the reaction activity and selectivity and figuring out that transition metal-catalyzed paired electrolysis is an important direction of organic electrochemistry in the future and offers numerous opportunities for new and improved organic reaction methods.

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation.     

Synthesis of novel bidentate P-chiral diaminophosphine oxide preligands: application to Pd-catalyzed asymmetric allylic substitution reactions

We developed a novel (S)-L-phenylalanine derived-bidentate chiral diaminophosphine oxide (DIAPHOX) preligand (S,S(P))-9b, which was successfully applied to Pd-catalyzed asymmetric allylic alkylation and amination. Using the Pd-(S,S(P))-9b catalyst system, asymmetric allylic alkylation and amination proceeded very smoothly, affording the corresponding products in excellent yield with high enantiomeric excess. It is noteworthy that both enantiomers were accessible with high enantiomeric purity using the structurally related DIAPHOX preligands (S,S(P))-9b and a monodentate chiral diaminophosphine oxide preligand (S,R(P))-10a, both of which can be prepared from a single chiral source, (S)-L-phenylalanine.     

Transition metal-catalyzed three-component coupling of allenes and the related allylation reactions

The feature article surveys the transition metal-catalyzed three-component coupling of allenes and the related allylation reactions. Most of the reactions shown in the article mechanistically proceed via oxidative addition of organic electrophiles to metals, followed by carbometallation of allene and then transmetalation by main group metals or reagents and organometallic reagents. These reactions provide an efficient route for the synthesis of various substituted allyl and vinyl metal reagents and complex organic molecules in highly regio-, stereo- and chemoselective manner in one pot. The metal reagents or pi-allyl-metal intermediates obtained from the reaction are utilized for the allylation of aldehydes, ketones and imines, producing various homoallylic alcohols and amines in a highly regio- and stereoselective manner.     

Modular asymmetric synthesis of P-chirogenic beta-amino phosphine boranes

A short concise route to beta-aminophosphine boranes is presented via the desymmetrization of prochiral phosphine boranes, forming P-chirogenic aldehydes that are rapidly transformed to the target compounds employing reductive amination under microwave irradiation. This sequence provides a modular route to P-chirogenic P,N ligands, and in addition, the intermediate aldehydes are versatile P-chiral building blocks for ligand design in general. An alternative pathway via the corresponding alpha-carboxyphosphines is also described. The ligands were subsequently evalutated in the asymmetric conjugate addition of diethylzinc to trans-beta-nitrostyrene.     

Toward green catalytic synthesis—Transition metal-catalyzed reactions in non-conventional media

Solvents play a critical role in “greening” synthetic chemistry, and this is also true in catalytic organic synthesis. This review attempts to summarize the progress made in the past a few years on homogeneous and heterogeneous catalytic reactions in the non-conventional solvents, water, ionic liquids, supercritical carbon dioxide and fluorous carbons, with the focus on those catalyzed by transition metal complexes. The reactions covered include hydrogenation, hydroformylation, carbonylation, Heck reactions, Suzuki and Stille couplings, Sonogashira reactions, allylic substitution, olefin metathesis, olefin epoxidation and alcohol oxidation.     

Transition metal-catalyzed reactions of propargylic carboxylates via an initial 1,2-acyloxy migration

Propargylic carboxylates, as a type of easily available alkyne compounds, have attracted considerable attentions in recent decade. Under the catalysis of transition metal complex (Pd, Ru, Pt, Au, Rh etc), one of chemical transformations of propargylic carboxylate is 1,2-acyloxy migration. The resultant alkenyl metallocarbenoid or metal-containing species may undergo a variety of chemical transformations, leading to formation of carbocyclic and heterocyclic compounds. In this review, representative domino reactions initiated by 1,2-acyloxy migration of propargylic carboxylates are summarized, including pentannuations, cycloadditions and rearrangements. Some mechanistic discussions and synthetic applications are also included.     

Transition metal-catalyzed carbon-carbon bond activation

This tutorial review deals with recent developments in the activation of C-C bonds in organic molecules that have been catalyzed by transition metal complexes. Many chemists have devised a variety of strategies for C-C bond activation and significant progress has been made in this field over the past few decades. However, there remain only a few examples of the catalytic activation of C-C bonds, in spite of the potential use in organic synthesis, and most of the previously published reviews have dwelt mainly on the stoichiometric reactions. Consequently, this review will focus mainly on the catalytic reaction of C-C bond cleavage by homogeneous transition metal catalysts. The contents include cleavage of C-C bonds in strained and unstrained molecules, and cleavage of multiple C-C bonds such as C[triple bond]C triple bonds in alkynes. Multiple bond metathesis and heterogeneous systems are beyond the scope of this review, though they are also fascinating areas of C-C bond activation. In this review, the strategies and tactics for C-C bond activation will be explained.     

Catalytic asymmetric phase-transfer reactions using tartrate-derived asymmetric two-center organocatalysts

A new highly versatile asymmetric two-center catalyst, tartrate-derived diammonium salt (TaDiAS), was designed and a catalyst library containing more than 70 new two-center catalysts was constructed. A variety of (S,S)- and (R,R)-TaDiAS were easily synthesized from diethyl l- and d-tartrate, respectively, using common and inexpensive reagents under operationally simple reaction conditions. TaDiAS was used in phase-transfer alkylations and Michael additions to afford various optically active α-amino acid equivalents in up to 93% yield. Moreover, dramatic counter anion effects were observed in phase-transfer catalysis (PTC) for the first time, making it possible to further improve reactivity and selectivity. These findings validate the usefulness of three-dimensional fine-tuning of the catalyst (acetal, Ar, and counter anion) for optimization. Recovery and reuse of the catalyst was also possible using simple procedures. The present asymmetric PTC was successfully applied to enantioselective syntheses of serine protease inhibitor aeruginosin 298-A and its analogues.     

Polyaniline-supported nano metal-catalyzed coupling reactions: Opportunities and challenges

Polyanilines (PANIs) can be easily prepared from the available and cheap anilines via the oxidative polymerization reactions. Owing to the coordination of nitrogen in the material with metals, PANIs are widely used as the support of nano metal catalysts. In comparison with inorganic supports, the nano metals on PANIs were firmly anchored via the coordination bond so that they are not easily to lose during the reaction process. Moreover, since PANIs are versatile materials and their chemical features can be adjusted by introducing functional groups onto the monomers, the catalytic activities of the prepared catalysts are tunable. During the past decade, PANIs-supported nano metal catalysts have been widely applied in a variety of coupling reactions. This review aims to summarize the recent advances and give a perspective.     

P-Chirogenic diaminophosphine oxide: a new class of chiral phosphorus ligands for asymmetric catalysis

We successfully synthesized a novel P-chirogenic diaminophosphine oxide 4, which was applied to catalytic enantioselective construction of quaternary carbon centers using Pd-catalyzed asymmetric allylic substitution with various beta-keto esters (up to 99% yield, 94% ee). Preliminary mechanistic studies indicated that two molecules of 8 coordinate to the Pd metal in a monodentate fashion, resulting in the formation of Pd complex 9 (Pd:8 = 1:2), which functions as the active species.     

Transition metal-catalyzed synthesis of pyrroles from dienyl azides

A range of 2,5-disubstituted and 2,4,5-trisubstituted pyrroles can be synthesized from dienyl azides at room temperature using catalytic amounts of ZnI2 or Rh2(O2CC3F7)4.