Regio- and Diastereoselective Annulation of α,ß-Unsaturated Aldimines with Alkenes via Allylic C(sp3)-H Activation by Rare-Earth Catalysts.

The [3 + 2] or [4 + 2] annulation of α,ß-unsaturated aldimines with alkenes via ß'- or γ-allylic C(sp3)-H activation is, in principle, an atom-efficient route for the synthesis of five- or six-membered-ring cycloalkylamines, which are important structural motifs in numerous natural products, bioactive molecules, and pharmaceuticals. However, such a transformation has remained undeveloped to date probably due to the lack of suitable catalysts. We report herein for the first time the regio- and diastereoselective [3 + 2] and [4 + 2] annulations of α,ß-unsaturated imines with alkenes via allylic C(sp3)-H activation by half-sandwich rare-earth catalysts having different metal ion sizes. The reaction of α-methyl-substituted α,ß-unsaturated aldimines with alkenes by a C5Me4SiMe3-ligated scandium catalyst took place in a trans-diastereoselective [3 + 2] annulation fashion via C(sp3)-H activation at the α-methyl group (ß'-position), exclusively affording alkylidene-functionalized cyclopentylamines with excellent trans-diastereoselectivity. In contrast, the reaction of ß-methyl-substituted α,ß-unsaturated aldimines with alkenes by a C5Me5-ligated cerium catalyst proceeded in a cis-diastereoselective [4 + 2] annulation fashion via γ-allylic C(sp3)-H activation, selectively yielding multisubstituted 2-cyclohexenylamines with excellent cis-diastereoselectivity. The mechanistic details of these transformations have been elucidated by deuterium-labeling experiments, kinetic isotope effect studies, and the isolation and transformations of key reaction intermediates. This work offers an efficient and selective protocol for the synthesis of a new family of cycloalkylamine derivatives, featuring 100% atom efficiency, high regio- and diastereoselectivity, broad substrate scope, and an unprecedented reaction mechanism.

Synthesis of Tough and Fluorescent Self-Healing Elastomers by Scandium-Catalyzed Terpolymerization of Pyrenylethenylstyrene, Ethylene, and Anisylpropylene.

The synthesis of fluorescent self-healing polymers by the incorporation of a fluorophore-containing olefin into a polyolefin backbone through catalyst-controlled multicomponent copolymerization is of fundamental interest and practical importance, but such an approach has remained unexplored to date. Herein, we report for the first time the synthesis of tough and fluorescent self-healing polymers by sequence-controlled terpolymerization of 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), ethylene (E), and anisylpropylene (AP) using a sterically demanding half-sandwich scandium catalyst. The resulting terpolymers consisted of relatively long alternating E-alt-AP sequences, isolated Pyr units, and short E-E blocks, which exhibited excellent tensile strength, remarkable self-healability, and high fluorescence quantum yield. The excellent mechanical and self-healing properties could be attributed to the nanophase separation of the crystalline E-E segments and the hard Pyr aggregates from a flexible E-alt-AP segment matrix, in which the Pyr units not only served as an efficient fluorophore but also played an important role in forming nanodomains and enhancing the polymer mobility. Furthermore, the styrenyl C═C bond of the Pyr unit in the terpolymers could undergo [2 + 2] cycloaddition under photoirradiation, which thus enabled the fabrication of a self-healable fluorescent two-dimensional image on a terpolymer film through photolithography. This work offers an unprecedented efficient protocol for the synthesis of a brand-new family of fluorescent self-healing materials, showcasing the high potential of catalyst-controlled sequence-regular copolymerization of different olefins for the creation of novel functional polymers.

Divergent Synthesis of Multi-Substituted Aminotetralins via [4+2] Annulation of Aldimines with Alkenes by Rare-Earth-Catalyzed Benzylic C(sp3 )-H Activation.

The search for efficient and selective methods for the divergent synthesis of multi-substituted aminotetralins is of much interest and importance. We report herein for the first time the diastereoselective [4+2] annulation of 2-methyl aromatic aldimines with alkenes via benzylic C(sp3 )-H activation by half-sandwich rare-earth catalysts, which constitutes an efficient route for the divergent synthesis of both trans and cis diastereoisomers of multi-substituted 1-aminotetralin derivatives from readily accessible aldimines and alkenes. The use of a scandium catalyst bearing a sterically demanding cyclopentadienyl ligand such as C5 Me4 SiMe3 or C5 Me5 exclusively afforded the trans-selective annulation products in the reaction of aldimines with styrenes and aliphatic alkenes. In contrast, the analogous yttrium catalyst, whose metal ion size is larger than that of scandium, yielded the cis-selective annulation products. This protocol features 100 % atom-efficiency, excellent diastereoselectivity, broad substrate scope, and good functional group compatibility. The reaction mechanisms have been elucidated by kinetic isotope effect (KIE) experiments and the isolation and transformations of some key reaction intermediates.

Enantioselective Synthesis of 1-Aminoindanes via [3 + 2] Annulation of Aldimines with Alkenes by Scandium-Catalyzed C-H Activation.

Multisubstituted chiral 1-aminoindanes are important components in many pharmaceuticals and bioactive molecules. Therefore, the development of efficient and selective methods for the synthesis of chiral 1-aminoindanes is of great interest and importance. In principle, the asymmetric [3 + 2] annulation of aldimines with alkenes through C-H activation is the most atom-efficient and straightforward route for the construction of chiral 1-aminoindanes, but such a transformation has remained undeveloped to date probably due to the lack of suitable catalysts. Herein, we report for the first time the enantioselective [3 + 2] annulation of a wide range of aromatic aldimines and alkenes via ortho-C(sp2)-H activation by chiral half-sandwich scandium catalysts, which provides a straightforward route for the synthesis of multisubstituted chiral 1-aminoindanes. This protocol features 100% atom-efficiency, broad functional group compatibility, and high regio-, diastereo-, and enantioselectivity (up to >19:1 dr and 99:1 er). Remarkably, by fine-tuning the sterics of the chiral ligand around the catalyst metal center, the diastereodivergent asymmetric [3 + 2] annulation of aldimines and styrenes has been achieved with a high level of diastereo- and enantioselectivity, offering an efficient method for the synthesis of both the trans and cis diastereomers of a novel class of chiral 1-aminoindane derivatives containing two contiguous stereocenters from the same set of starting materials. Moreover, the asymmetric [3 + 2] annulation of aldimines with aliphatic α-olefins, norbornene, and 1,3-dienes has also been achieved.

Diastereo- and Enantioselective Hydrophosphination of Cyclopropenes under Lanthanocene Catalysis.

The asymmetric hydrophosphination of cyclopropenes with phosphines is of much interest and importance, but has remained hardly explored to date probably because of the lack of suitable catalysts. We report here the diastereo- and enantioselective hydrophosphination of 3,3-disubstituted cyclopropenes with phosphines by a chiral lanthanocene catalyst bearing the C2 -symmetric 5,6-dioxy-4,7-trans-dialkyl-substituted tetrahydroindenyl ligands. This protocol offers a selective and efficient route for the synthesis of a new family of chiral phosphinocyclopropane derivatives, featuring 100 % atom efficiency, good diastereo- and enantioselectivity, broad substrate scope, and no need for a directing group.

Auto-Tandem Copper-Catalyzed Carboxylation of Undirected Alkenyl C-H Bonds with CO2 by Harnessing ß-Hydride Elimination.

The exploration into challenging scenarios of the application of elementary reactions offers excellent opportunities for the development of unique transformations under organometallic catalysis. As a ubiquitous reaction of metal alkyl complexes, ß-hydride elimination plays a crucial role in a number of important catalytic transformations. However, its functions in these catalytic cycles are limited to either releasing alkene products or generating isomerized intermediates through further migratory insertion. Herein, we report that the precise manipulation of ß-hydride elimination enables an auto-tandem copper catalysis for the carboxylation of undirected alkenyl C-H bonds with CO2. In this transformation, ß-hydride elimination of an alkyl copper intermediate is facilitated, while its reaction with CO2 is suppressed. The resulting copper hydride in turn reacts with CO2 to provide access to a multitasking catalyst, which enables the tandem borylation/carboxylation of C-H bonds in two mechanistically distinct catalytic cycles.

Making Polyisoprene Self-Healable through Microstructure Regulation by Rare-Earth Catalysts.

The creation of self-healing polymers from commodity olefins is of great interest and importance but has remained a challenge to date. We report here for the first time the synthesis of self-healing polymers by catalyst-controlled polymerization of a simple commodity diene, isoprene. We found that polyisoprenes having an appropriate mixture (ca. 70/30) of 3,4- and cis-1,4-microstructures synthesized by using a half-sandwich scandium catalyst could act as excellent self-healing elastomers without any external intervention. The unprecedented self-healability could be ascribed to nanoscale heterogeneities formed by microphase separation of the relatively hard 3,4-segments from a flexible cis-1,4-segment matrix. The hydrogenated polyisoprenes (without C=C bonds) with the analogous microstructures also exhibited excellent mechanical and self-healing properties, further demonstrating that even simple polyolefins can be made self-healable if the microstructures are appropriately regulated.

Regio- and Diastereoselective Formal [2+2] Cycloaddition of Allenes with Amino-Functionalized Alkenes by Rare-Earth-Catalyzed C(sp2 )-H Activation.

The [2+2] cycloaddition of allenes with alkenes is of much interest and importance as a straightforward route for the construction of four-membered carbocycles but has remained much underexplored to date. Herein we report for the first time the intermolecular regio- and diastereoselective formal [2+2] cycloaddition of a wide range of allenes with amino-functionalized alkenes by half-sandwich rare-earth catalysts. The reaction proceeded through an allene C(sp2 )-H activation mechanism initiated by the site-selective deprotonation of the allene unit by a rare-earth metal alkyl species followed by alkene insertion into the resulting metal-allenyl bond and the subsequent intramolecular cycloaddition to an allene C=C bond. This protocol offers a unique route for the synthesis of a new family of cyclobutane and cyclobutene derivatives which were difficult to access previously.

Synthesis of allylanilines via scandium-catalysed benzylic C(sp3)-H alkenylation with alkynes.

The ortho-selective benzylic C(sp3)-H alkenylation of 2-methyl tertiary anilines with internal alkynes has been achieved for the first time by using a half-sandwich scandium catalyst. This protocol provides a straightforward route for the synthesis of a new family of 2-allylaniline derivatives, featuring broad substrate scope, 100% atom-efficiency, high yields, and high chemo-, regio-, and stereoselectivity.

Regio- and Diastereoselective [3+2] Annulation of Aliphatic Aldimines with Alkenes by Scandium-Catalyzed ß-C(sp3 )-H Activation.

Here we report for the first time the regio- and diastereoselective [3+2] annulation of a wide range of aliphatic aldimines with alkenes via the activation of an unactivated ß-C(sp3 )-H bond by half-sandwich scandium catalysts. This protocol offers a straightforward and atom-efficient route for the synthesis of a new family of multi-substituted aminocyclopentane derivatives from easily accessible aliphatic aldimines and alkenes. The annulation of aldimines with styrenes exclusively afforded the 5-aryl-trans-substituted 1-aminocyclopentane derivatives with excellent diastereoselectivity through the 2,1-insertion of a styrene unit. The annulation of aldimines with aliphatic alkenes selectively gave the 4-alkyl-trans-substituted 1-aminocyclopentane products in a 1,2-insertion fashion. A catalytic amount of an appropriate amine such as adamantylamine (AdNH2 ) or dibenzylamine (Bn2 NH) showed significant effects on the catalyst activity and stereoselectivity.

Terpolymerization of Ethylene and Two Different Methoxyaryl-Substituted Propylenes by Scandium Catalyst Makes Tough and Fast Self-Healing Elastomers.

The terpolymerization of a non-polar olefin (such as ethylene) and two different polar functional olefins in a controlled fashion is of great interest and importance but has hardly been explored to date. We report for the first time the terpolymerization of ethylene (E) and two different methoxyaryl-substituted propylenes (AR1 P=hexylanisyl propylene; AR2 P=methoxynaphthyl propylene or methoxypyrenyl propylene) by a half-sandwich scandium catalyst. The terpolymerization took place in a sequence-controlled fashion, affording unique multi-block copolymers composed of two different ethylene-alt-methoxyarylpropylene sequences E-alt-AR1 P (soft segments) and E-alt-AR2 P (hard segments) and relatively short ethylene-ethylene (EE) blocks (crystalline segments). The terpolymers exhibited excellent elasticity and unprecedented self-healing as a result of microphase separation of nanodomains of the crystalline EE segments and the hard amorphous E-alt-AR2 P segments from a very flexible E-alt-AR1 P matrix, demonstrating unique synergy of the three different components.

Modular Access to Spiro-dihydroquinolines via Scandium-Catalyzed Dearomative Annulation of Quinolines with Alkynes.

The catalytic enantioselective construction of three-dimensional molecular architectures from planar aromatics such as quinolines is of great interest and importance from the viewpoint of both organic synthesis and drug discovery, but there still exist many challenges. Here, we report the scandium-catalyzed asymmetric dearomative spiro-annulation of quinolines with alkynes. This protocol offers an efficient and selective route for the synthesis of spiro-dihydroquinoline derivatives containing a quaternary carbon stereocenter with an unprotected N-H group from readily accessible quinolines and diverse alkynes, featuring high yields, high enantioselectivity, 100% atom-efficiency, and broad substrate scope. Experimental and density functional theory studies revealed that the reaction proceeded through the C-H activation of the 2-aryl substituent in a quinoline substrate by a scandium alkyl (or amido) species followed by alkyne insertion into the Sc-aryl bond and the subsequent dearomative 1,2-addition of the resulting scandium alkenyl species to the C═N unit in the quinoline moiety. This work opens a new avenue for the dearomatization of quinolines, leading to efficient and selective construction of spiro molecular architectures that were previously difficult to access by other means.

Enantioselective C-H Alkenylation of Ferrocenes with Alkynes by Half-Sandwich Scandium Catalyst.

The enantioselective C-H alkenylation of ferrocenes with alkynes is, in principle, a straightforward and atom-efficient route for the construction of planar-chiral ferrocene scaffolds bearing alkene functionality but has remained scarcely explored to date. Here we report for the first time the highly enantioselective C-H alkenylation of quinoline- and pyridine-substituted ferrocenes with alkynes by a half-sandwich scandium catalyst. This protocol features broad substrate scope, high enantioselectivity, and 100% atom efficiency, selectively affording a new family of planar-chiral ferrocenes bearing N/alkene functionalities. The mechanistic details have been clarified by DFT analyses. The use of a quinoline/alkene-functionalized ferrocene product as a chiral ligand for asymmetric catalysis is also demonstrated.

Regiodivergent C-H Alkylation of Quinolines with Alkenes by Half-Sandwich Rare-Earth Catalysts.

The regiodivergent catalysis of C-H alkylation with alkenes is of great interest and importance but has remained hardly explored to date. We report herein the first regiodivergent C-H alkylation of quinolines with alkenes by half-sandwich rare-earth catalysts. The regiodivergence was achieved by fine-tuning the metal/ligand combination or steric and electronic properties of the catalysts. The use of the C5Me5-ligated scandium catalyst Sc-3 for the reaction of quinolines with styrenes and that of the C5Me4H-ligated yttrium catalyst Y-2 for the reaction with aliphatic olefins exclusively afforded the corresponding C8-H alkylation products, thus constituting the first example of direct C8-H alkylation of neutral quinolines. In contrast, the Sc-3-catalyzed reaction of 2-arylquinolines with aliphatic olefins and the Y-2-catalyzed reaction with styrenes selectively gave the 2-aryl o-C-H alkylation products. On the basis of the catalyst/substrate-controlled regiodivergence, the sequential regiospecific dialkylation of quinolines with two different alkenes has also been achieved. DFT studies revealed that the C-H activation of 2-phenylquinoline at both the C8 position and an ortho position of the 2-phenyl substituent was possible, and these two types of initially formed C-H activation products were interconvertible through the coordination and C-H activation of another molecule of quinoline. The regioselectivity for the C-H alkylation reactions was governed not only by the ease of the initial formation of the C-H activation products but also by the energy barriers for their interconversions, as well as by the energy barriers or steric and electronic influences in the subsequent alkene insertion processes. This work has not only constituted an efficient protocol for the selective synthesis of diversified quinoline derivatives but also offered unprecedented insights into the C-H activation and transformation of quinolines and may help in the design of more efficient, selective, or complementary catalysts.

Diastereodivergent [3 + 2] Annulation of Aromatic Aldimines with Alkenes via C-H Activation by Half-Sandwich Rare-Earth Catalysts.

Stereodivergent catalysis is of great importance, as it can allow efficient access to all possible stereoisomers of a given product with multiple stereocenters from the same set of starting materials. We report herein the first diastereodivergent [3 + 2] annulation of aromatic aldimines with alkenes via C-H activation by half-sandwich rare-earth catalysts. This protocol provides an efficient and general route for the selective synthesis of both trans and cis diastereoisomers of multisubstituted 1-aminoindanes from the same set of aldimines and alkenes, featuring 100% atom efficiency, excellent diastereoselectivity, broad substrate scope, and good functional group compatibility. The diastereodivergence is achieved by fine-tuning the sterics or ligand/metal combination of the half-sandwich rare-earth metal complexes.

Co-syndiospecific Alternating Copolymerization of Functionalized Propylenes and Styrene by Rare-Earth Catalysts.

The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of functional polymers, but studies toward this goal have met with only limited success to date. Now, the co-syndiospecific alternating copolymerization of methoxyphenyl- and N,N-dimethylaminophenyl-functionalized propylenes with styrene by half-sandwich rare-earth catalysts is reported. This reaction efficiently afforded the corresponding functionalized propylene-alt-styrene copolymers with a perfect alternating sequence and excellent co-syndiotacticity (rrrr >99 %), thus constituting the first example of co-stereospecific alternating copolymerization of polar and non-polar olefins.

Rare-Earth-Catalyzed C-H Silylation of Aromatic Heterocycles with Hydrosilanes.

The catalytic C-H silylation of a variety of aromatic heterocycles such as furan, pyrrole and thiophene derivatives with secondary hydrosilanes has been achieved by using an yttrium metallocene complex. This protocol provides an efficient and straightforward way for the synthesis of a series of silylated heteroaromatic compounds containing tertiary silane moieties without the need for an additive or H2 acceptor.

CO2 Activation by Lewis Pairs Generated Under Copper Catalysis Enables Difunctionalization of Imines.

Integration of distinct substrate activation modes in a catalytic circle is critical for the development of new, powerful synthetic methodologies toward complex and value-added chemicals from simple and readily available feedstocks. Here, we describe a highly selective difunctionalization of imines through incorporation of activation of CO2 by intramolecular N/B Lewis pairs into a copper catalytic cycle. Experimental and computational studies on the mechanistic aspect revealed an α-borylalkylamido intermediate, a metal amide-based Lewis pair formed by borylation of a C-N double bond, and enabled an unprecedented CO2 fixation pattern that is in sharp contrast to the traditional CO2 insertion into transition-metal-element bonds. The unique lithium cyclic boracarbamate products could be easily transformed into multifunctional N-carboxylated α-amino boronates. The highly diastereoselective reactions of chiral N-tert-butanesulfinyl aldimines were also achieved. We hope that our findings may inspire further development of selective multicomponent reactions by incorporation of Lewis pair chemistry into transition-metal catalysis.

Construction of All-Carbon Quaternary Stereocenters by Scandium-Catalyzed Intramolecular C-H Alkylation of Imidazoles with 1,1-Disubstituted Alkenes.

The exo-selective C-H cycloaddition of imidazoles to 1,1-disubstituted alkenes has been achieved for the first time by using half-sandwich scandium catalysts. A wide range of imidazole compounds bearing various 1,1-disubstituted aliphatic alkenes, styrenes, dienes, and enynes have been selectively converted in high yields to the corresponding bicyclic imidazole derivatives bearing ß-all-carbon-substituted quaternary stereocenters. By using a chiral half-sandwich scandium catalyst, the asymmetric exo-selective cyclization has also been achieved with a high level of enantioselectivity.

A new simultaneous measurement system of wide Q-range small angle neutron scattering combined with polarized Fourier transform infrared spectroscopy.

Small angle neutron scattering (SANS) is a versatile and convenient method to investigate the higher order structure of molecular assembly systems. However, the more complicated a system of interest, the more difficult the interpretation in the SANS profile. In order to increase the reliability of structural analysis on a complicated system, it is desirable to obtain different kinds of structural information from the same sample simultaneously. Polarized infrared spectroscopy is able to provide information about the molecular structure, concentration, and orientation of each chemical species in a system. In order to utilize these advantages of polarized infrared spectroscopy, a simultaneous measurement system was built by incorporating a Fourier transform infrared (FTIR) spectrometer into a time-of-flight small angle neutron scattering instrument covering a wide Q range. Using this system, simultaneous measurements of wide- and small-angle neutron scattering and polarized FTIR spectroscopy was realized for the first time.