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Summary Ligand-controlled reactivity plays an important role in transition-metal catalysis, enabling a vast number of efficient transformations to be discovered and developed. However, a single ligand is generally used to promote all steps of the catalytic cycle (e.g., oxidative addition, reductive elimination), a requirement that makes ligand design challenging and limits its generality, especially in relay asymmetric transformations. We hypothesized that multiple ligands with a metal center might be used to sequentially promote multiple catalytic steps, thereby combining complementary catalytic reactivities through a simple combination of simple ligands. With this relay catalysis strategy (L/L∗), we report here the first highly regio- and enantioselective remote hydroarylation process. By synergistic combination of a known chain-walking ligand and a simple asymmetric cross-coupling ligand with the nickel catalyst, enantioenriched α-aryl alkylboronates could be rapidly obtained as versatile synthetic intermediates through this formal asymmetric remote C(sp3)-H arylation process.

We here present a generally applicable cobalt-catalyzed remote hydroboration of alkenyl amines, providing a practical strategy for the preparation of borylamines and aminoalcohols. This method shows broad substrate scope and good functional group tolerance, tolerating a series of alkenyl amines, including alkyl-alkyl amines, alkyl-aryl amines, aryl-aryl amines, and amides. Of note, this protocol is also compatible with a variety of natural products and drug derivatives. Preliminary mechanistic studies suggest that this transformation involves an iterative chain walking and hydroboration sequence.

Pd-catalyzed reaction of olefins is sometimes accompanied by isomerization of the Pd center along the aliphatic chain (chain walking). The chain walking reaction enables synthesis of polyolefins wi...

In recent years, polyolefin elastomers play an increasingly important role in industry. The late transition metal complex catalysts, especially α-diimine Ni(II) and α-diimine Pd(II) complex catalysts, are popular “chain-walking” catalysts. They can prepare polyolefin with various structures, ranging from linear configuration to highly branched configuration. Combining the “chain-walking” characteristic with different polymerization strategies, polyolefins with good elasticity can be obtained. Among them, olefin copolymer is a common way to produce polyolefin elastomers. For instance, strictly defined diblock or triblock copolymers with excellent elastic properties were synthesized by adding ethylene and α-olefin in sequence. As well as the incorporation of polar monomers may lead to some unexpected improvement. Chain shuttling polymerization can generate multiblock copolymers in one pot due to the interaction of the catalysts with chain shuttling agent. Furthermore, when regarding ethylene as the sole feedstock, owing to the “oscillation” of the ligands of the asymmetric catalysts, polymers with stereo-block structures can be generated. Generally, the elasticity of these polyolefins mainly comes from the alternately crystallineamorphous block structures, which is closely related to the characteristic of the catalytic system. To improve performance of the catalysts and develop excellent polyolefin elastomers, research on the catalytic mechanism is of great significance. Electron spin resonance (ESR), as a precise method to detect unpaired electron, can be applied to study transition metal active center. Therefore, the progress on the exploration of the valence and the proposed configuration of catalyst active center in the catalytic process by ESR is also reviewed.

Organozirconium chemistry has found extensive applications in organic synthesis since its discovery in the last century. Alkyl­zirconocenes, which are easily generated by the hydrozirconation of alkenes with the Schwartz reagent, are widely utilized for carbon–carbon­ and carbon–heteroatom bond formation. This short review summarizes the progress to date on the applications alkylzirconocenes in organic synthesis.1 Introduction2 General Methods for Generating Alkylzirconocenes3 Transformations of Alkylzirconocenes by Heteroatoms4 Insertion of Unsaturated Groups into Alkylzirconocenes5 Transmetalations6 Cross-Coupling Reactions of Alkylzirconocenes7 Photochemistry of Alkylzirconocenes8 Bimetallic Reagents of Zirconium9 Asymmetric Transformations10 Applications of Alkylzirconocenes Generated from the Negishi Reagent11 Conclusions and Outlook

The ternary Pd complexes [(phen)Pd(H)]+ (1-Pd) and [(phen)Pd(CH3)]+ (5-Pd) (where phen = 1,10-phenanthroline) both react with hexane in a linear ion trap mass spectrometer, forming the C–H activation product [(phen)Pd(C6H11)]+ (3-Pd) and releasing H2 and CH4, respectively. Density functional theory (DFT) calculations agree well with the experiments in predicting low barriers for these reactions proceeding via a metathesis mechanism. Species 3-Pd undergoes extensive fragmentation, or "cracking", of the hydrocarbon chain when sufficient energy is supplied via collision-induced dissociation (CID), resulting in the extrusion of a mixture of alkenes, methane, and hydrogen. DFT calculations show that Pd "chain-walking" from α (terminal carbon) to β and from β to γ positions can proceed with barriers sufficiently below those required for chain "cracking". The fragmentation reactions can be made catalytic if 1-Pd and 5-Pd produced by CID of 3-Pd are allowed to react with hexane again. Ni complexes largely mirrored the chemistry observed for Pd. Both 1-Ni and 5-Ni reacted with hexane, forming 3-Ni, which fragmented under CID conditions in a fashion similar to 3-Pd. In contrast, only 5-Pt reacted with hexane to form 3-Pt, which fragmented predominantly via sequential losses of H2.

Polyolefin waste is constantly growing, and the few existing solutions for recycling, reuse, and degradation are not viable long term. Carbon–carbon bond scission is a highly sought-after technology to assist in reclaiming polymers. This work compiles and advances the understanding of β-alkyl elimination, a method of C–C cleavage, through DFT characterization on a model substrate, (S)-2,8-dimethyldecane, and silica-supported Zr–H catalyst, [(SiO)3ZrH]. The primary goal is to examine selectivity in C–C bond cleavage events. σ-Bond metathesis favors C–H activation at methyl branches by ∼2 kcal mol−1. Chain walking via β-H elimination and insertion occurs readily and prefers E-alkene eliminations. β-Alkyl elimination also favors formation of E-alkene elimination products (∼2 kcal mol−1), β-Me elimination (∼1 kcal mol−1), and primary Zr–C cleavage (∼2 kcal mol−1) over Z-alkenes, β-R (R > CH3) elimination, and secondary Zr–C cleavage, respectively. These selectivity rules will help guide future experimental work and catalyst design.

Past several decades have witnessed the great evolution of inert C–H bond functionalization reactions as an emerging technique for synthesizing drug molecules, agrochemicals, and functional materials with intricate three-dimensional architectures. Although most activation of “unreactive” C–H bonds was accomplished by exploiting the power of transition metal catalysts, the distant and selective activation of unreactive C–H bonds in an undirected fashion remains one of the critical challenges to this rapidly growing field of organic chemistry. In this context, to meet all these concerns, much more attractive and challenging transition metal catalytic transformations have begun to blossom in recent years with the aid of the chain-walking process. The chain-walking strategy is one of the state-of-the-art techniques in organic synthesis to functionalize the unreactive C–H bonds by allowing the movement of a metal complex along the hydrocarbon chain of the substrate to recognize preferable bond-forming sites. The essential advantage of this strategy is that the bonds are formed only at the places where the catalyst selects for the specific C–H bonds to be cleaved, which not only avoids tedious synthetic procedures for prefunctionalization and the emission of undesirable wastes but also inspires chemists to plan novel synthetic strategies in a completely different manner. Consequently, various C–H bond functionalization reactions have been reported in recent years, employing the vast opportunity provided by this growing field mainly for the acyclic olefinic systems with flexible alkyl chains. Thus, chain-walking reactions allow the reactivity of the reaction centers within the substrates that cannot be realized via the classical mode of reactivity of the substrates. Applying this approach, inexpensive feedstock materials and simple hydrocarbons as an isomeric mixture can be converted to a single isomeric product in a regioconvergent scenario. Simultaneously, the site-selectivity of these reactions can also be switched using a regiodivergent strategy via appropriate tuning of ligands or a slight modification of reaction conditions. Herein, we have provided a comprehensive overview of the chain-walking reactions involving a variety of catalytic systems ranging from the first-row transition metal catalysts to the third-row transition metal catalysts for C–H activation in a concise fashion with the hope for further developments in this area through the appropriate application of the chain-walking reactions.

Benefiting from the unique chain walking characteristic of late transition metal complexes, branched EPR-like elastomers bearing distinct differences compared to traditional linear EPRs are reported herein. Firstly, a series of acenaphthene-based α-diimine nickel complexes were prepared and thoroughly characterized. The single crystal structures of rac-Ni4 and rac-Ni5 were further determined by X-ray crystallography, in which intra-ligand π–π interactions could be clearly observed. Being activated by Et3Al2Cl3, rac-Ni1–Ni5 are able to promote propylene homopolymerization and copolymerization with ethylene with high catalytic activities, affording EPR-like products with unique branched structures and sequences. Through regulating polymerization parameters (temperature, monomer feeding ratio, etc.) and ligand structures that play a pivotal role in governing the chain walking abilities of the precatalyst, obviously different polymer products were obtained respectively from propylene homopolymerization and ethylene/propylene copolymerization. The former case afforded products with predominant P units, whereas the latter case gave rise to copolymers with predominant E units. Furthermore, dramatic changes in the P and E unit contents as well as their sequences were observed along with the variation in polymerization temperature.

This work explores the mechanism whereby a cationic diimine Pd(II) complex combines coordination insertion and radical polymerization to form polyolefin-polar block copolymers. The initial requirement involves the insertion of a single acrylate monomer into the Pd(II)-polyolefin intermediates, which generate a stable polymeric chelate through a chain-walking mechanism. This thermodynamically stable chelate was also found to be photochemically inactive, and a unique mechanism was discovered which allows for radical polymerization. Rate-determining opening of the chelate by an ancillary ligand followed by additional chain walking allows the metal to migrate to the α-carbon of the acrylate moiety. Ultimately, the molecular parameters necessary for blue-light-triggered Pd-C bond homolysis from this α-carbon to form a carbon-centered macroradical species were established. This intermediate is understood to initiate free radical polymerization of acrylic monomers, thereby facilitating block copolymer synthesis from a single Pd(II) complex. Key intermediates were isolated and comprehensively characterized through exhaustive analytical methods which detail the mechanism while confirming the structural integrity of the polyolefin-polar blocks. Chain walking combined with blue-light irradiation functions as the mechanistic switch from coordination insertion to radical polymerization. On the basis of these discoveries, robust di- and triblock copolymer syntheses have been demonstrated with olefins (ethylene and 1-hexene) which produce amorphous or crystalline blocks and acrylics (methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate) in broad molecular weight ranges and compositions, yielding AB diblocks and BAB triblocks.

Polyolefins are produced in vast amounts and are found in so many consumer products that the two most commonly produced forms, polyethylene (PE) and polypropylene (PP), fall into the rather sparse category of molecules that are likely to be known by people worldwide, regardless of their occupation. Although widespread, the further upgrading of their properties (mechanical, physical, aesthetic, etc.) through the formation of composites with other materials, such as polar polymers, fibers, or talc, is of huge interest to manufacturers. To improve the affinity of polyolefins toward these materials, the inclusion of polar functionalities into the polymer chain is essential. The incorporation of a functional group to trigger controlled polymer degradation is also an emerging area of interest. Currently practiced methods for the incorporation of polar functionalities, such as post-polymerization functionalization, are limited by the number of compatible polar monomers: for example, grafting maleic anhydride is currently the sole method for practical functionalization of PP. In contrast, the incorporation of fundamental polar comonomers into PE and PP chains via coordination insertion polymerization offers good control, making it a highly sought-after process. Early transition metal catalysts (which are commonly used for the production of PE and PP) display poor tolerance toward the functional groups within polar comonomers, limiting their use to less-practical derivatives. As late transition metal catalysts are less-oxophilic and thus more tolerant to polar functionalities, they are ideal candidates for these reactions. This Account focuses on the copolymerization of propylene with polar comonomers, which remains underdeveloped as compared to the corresponding reaction using ethylene. We begin with the challenges associated with the regio- and stereoselective insertion of propylene, which is a particular problem for late transition metal systems because of their propensity to undergo chain walking processes. To overcome this issue, we have investigated a range of metal/ligand combinations. We first discuss attempts with group 4 and 8 metal catalysts and their limitations as background, and then focus on the copolymerization of propylene with methyl acrylate (MA) using Pd/imidazolidine-quinolinolate (IzQO) and Pd/phosphine-sulfonate (PS) precatalysts. Each generated regioregular polymer, but while the system featuring an IzQO ligand did not display any stereocontrol, that using the chiral PS ligand did. A further difference was found in the insertion mode of MA: the Pd/IzQO system inserted in a 1,2 fashion, while in the Pd/PS system a 2,1 insertion was observed. We then move onto recent results from our lab using Pd/PS and Pd/bisphosphine monoxide (BPMO) precatalysts for the copolymerization of propylene with allyl comonomers. These P-stereogeneic precatalysts generated the highest isotacticity values reported to date using late transition metal catalysts. This section closes with our work using Earth-abundant nickel catalysts for the reaction, which would be especially desired for industrial applications: a Ni/phosphine phenolate (PO) precatalyst yielded regioregular polypropylene with the incorporation of some allyl monomers into the main polymer chain. The installation of a chiral menthyl substituent on the phosphine allowed for moderate stereoselectivity to be achieved, though the applicable polar monomers currently remain limited. The Account concludes with a discussion of the factors that affect the insertion mode of propylene and polar comonomers in copolymerization reactions, beginning with our recent computational study, and finishing with work from ourselves and others covering both comonomer and precatalyst steric and electronic profiles with reference to the observed regioselectivity.

A regiodivergent nickel-catalyzed hydrocyanation of a broad range of internal alkenes involving a chain-walking process is reported. When appropriate diastereomeric biaryl diphosphite ligands are applied, the same starting materials can be converted to either linear or branched nitriles with good yields and high regioselectivities. DFT calculations suggested that the catalyst architecture determines the regioselectivity by modulating electronic and steric interactions. In addition, moderate enantioselectivities were observed when branched nitriles were produced.

Copolymerization of functionalized vinyl monomers with olefin is extraordinarily important to provide value-added polar polyolefins. A study on the reactivity of functionalized vinyl monomers enabl...

Metal-catalyzed chain-walking reactions have recently emerged as a powerful strategy to functionalize remote positions in organic molecules. However, a chain-walking protocol for nonconjugated dienes remains scarcely reported, and developments are currently ongoing. In this Communication, a nickel-catalyzed asymmetric hydrocyanation of nonconjugated dienes involving a chain-walking process is demonstrated. The reaction exhibits excellent regio- and chemoselectivity, and a wide range of substrates were tolerated, delivering the products in high yields and enantioselectivities. Deuterium-labeling experiments support the chain-walking process, which involves an iterative β-H elimination and reinsertion processes. Gram-scale synthesis, regioconvergent experiments, and downstream transformations gave further insights into the high potential of this transformation.

Despite remarkable recent advances in transition-metal-catalyzed C(sp3)−C cross-coupling reactions, there remain challenging bond formations. One class of such reactions include the formation of tertiary-C(sp3)−C bonds, presumably due to unfavorable steric interactions and competing isomerizations of tertiary alkyl metal intermediates. Reported herein is a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary centers. This approach enables the facile construction of otherwise difficult to prepare all-carbon quaternary centers. Key to the success of this transformation is an unusual remote functionalization via chain walking to the most sterically hindered tertiary C(sp3) center of the substrate. Preliminary mechanistic and radical trapping studies with primary alkyl bromides suggest a unique mode of tertiary C-radical generation through chain-walking followed by Ni–C bond homolysis. This strategy is complementary to the existing coupling protocols with tert-alkyl organometallic or -alkyl halide reagents, and it enables the expedient formation of quaternary centers from easily available starting materials., Formation of tertiary C(sp3)-C bonds is a formidable challenge due to steric interactions and low barriers for isomerization of intermediates. Here, the authors show a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary carbon centers.

Chain-walking is a powerful approach toward the functionalization of C–H bonds remote to a functional group. Whereas various Pd-catalyzed migratory cross-couplings have been developed in the past years, the design of an efficient migratory version of the popular Suzuki–Miyaura cross-coupling has remained elusive. The current article reports a one-pot procedure consisting of alkene hydroboration and migratory Suzuki–Miyaura coupling of the resulting alkylboronic acid intermediate. A high regioselectivity for the benzylic position of the initial alkene was achieved by using P(t-Bu)2Me as the ligand and an ortho-substituted aryl electrophile. Regioconvergence from alkene positional and geometrical isomers and long-range migration were demonstrated. Mechanistic investigations indicated that the migration occurs through a partially reversible, nondissociative mechanism.

We report a newly developed, palladium-catalyzed dehydrosilylation of terminal alkylsilanes that combines with chain-walking hydrosilylation to create a one-pot isomerization of internal olefins to...

Branched polyolefin microstructures resulting from so‐called “chain walking” are a fascinating feature of late transition metal catalysts; however, to date it has not been demonstrated how desirable branched polyolefin microstructures can be generated thereby. We demonstrate how highly branched polyethylenes with methyl branches (220 Me/1000 C) exclusively and very high molecular weights (ca. 106 g mol−1), reaching the branch density and microstructure of commercial ethylene–propylene elastomers, can be generated from ethylene alone. At the same time, polar groups on the main chain can be generated by in‐chain incorporation of methyl acrylate. Key to this strategy is a novel rigid environment in an α‐diimine PdII catalyst with a steric constraint that allows for excessive chain walking and branching, but restricts branch formation to methyl branches, hinders chain transfer to afford a living polymerization, and inverts the regioselectivity of acrylate insertion to a 1,2‐mode., Contradiction resolution: The contradictive event of abundant branch formation and in‐chain incorporation of polar functional groups in “chain walking” olefin polymerization has been resolved using a novel catalyst, which enables the generation of high‐molecular‐weight ethylene–propylene elastomers from ethylene exclusively, with ultrahigh branching (methyl branches exclusively: 220 Me/1000 C) and in‐chain incorporation of methyl acrylate.

The direct and chemoselective conversion of the carbon-metal bond of gem-dimetallic reagents enables rapid and sequential formation of multiple carbon-carbon and carbon-heteroatom bonds, thus representing a powerful method for efficiently increasing structural complexity. Herein, we report a visible-light-induced, nickel-catalyzed, chemoselective cross-coupling reaction between gem-borazirconocene alkanes and diverse aryl halides, affording a wide range of alkyl Bpin derivatives in high yields with excellent regioselectivity. This practical method features attractively simple reaction conditions and a broad substrate scope. Additionally, we systematically investigated a Bpin-directed chain walking process underlying the regioselectivity of alkylzirconocenes, thus uncovering the mechanism of the remote functionalization of internal olefins achieved with our method. Finally, DFT calculations indicate that the high regioselectivity of this reaction originates from the directing effect of the Bpin group.

Chain-walking (CW) catalysis applied to α-olefin polymerization gives rise to structurally unparalleled macromolecules with diverse topological and rheological properties. The specific motion patte...

We report an efficient catalytic synthesis of “necklace” polymers, polyethylene (PE) denpols, utilizing the chain-walking polymerization (CWP). The approach is based on the design of a linear multivalent chain-walking catalyst that can initiate hyperbranched polymerization of ethylene for in situ formation of multiple dendritic PEs covalently tethered to the linear polymer backbone. The simplicity and efficiency of this approach makes it promising for facile preparation of large soluble nanostructures for various potential applications.

Angewandte Chemie / International edition 61(1), e202113667 (2022). doi:10.1002/anie.202113667, Published by Wiley-VCH, Weinheim

The efficient cobalt-catalyzed remote hydroboration and alkene isomerization of allylic siloxanes with pinacolborane were realized by a ligand-controlled strategy. With 1,2-bis(dicyclohexyl-phosphino)ethane as the ligand, the remote hydroboration reactions proceeded well via a tandem chain walking/hydroboration process, affording synthetically useful borylethers with good efficiency. Whereas, the use of xantphos favored the formation of silyl enol ethers via alkene isomerization. It represents a rare example of modulating the direction of chain walking by a ligand-controlled strategy.

A novel method for catalytic remote bismetalation of alkene substrates by the addition of dimetal reagents is accomplished by using chain walking. In the presence of a palladium catalyst, the reaction of various 1,n-dienes and diborons were converted into cyclopentane derivatives with two boryl groups at remote positions via facile regioselective transformation of an unactivated sp3 C-H bond to a C-B bond. Sequential construction of three distant bonds, which is difficult to achieve by any method, was accomplished for the reactions of 1,n-dienes (n ≥ 7).

Summary Transition-metal-catalyzed cross-coupling reactions between naturally abundant sp3-hybridized carbon centers facilitate access to diverse molecules with complex three-dimensional structures. Organometallic compounds are among one of the most powerful reagents that are broadly used in carbon–carbon bond formations. Although sp2-hybridized organometallic compounds are widely employed in cross-couplings, sp3-hybridized organometallic coupling partners are less developed. Herein, we report visible-light-induced single nickel-catalyzed C(sp3)–C(sp3), C(sp3)–C(sp2), and C(sp3)–C(sp) cross-coupling reactions using alkylzirconocenes, which are easily generated in situ from terminal or internal unactivated alkenes through hydrozirconation and chain walking. This method is mild and applicable for a large range of substrates including primary, secondary, tertiary alkyl, aryl, alkenyl, alkynyl halides, and a variety of alkenes. Mechanistic studies suggest a novel nickel-catalyzed radical cross-coupling pathway, which represents the first visible-light-induced transformation of alkylzirconocenes.

We present a new strategy to regulate branching in chain-walking olefin polymerization by triggering a rapid isomerization of 1-alkene monomers into internal olefins by adding a Lewis acid. Polymerization of internal alkenes proceeds via chain-walking to give polymers with much higher branching than 1-alkene analogues. The utility of this approach is exemplified by synthesis of well-defined block copolymers with distinct branching characteristics per block by addition of Lewis acid midway through a reaction. We propose a novel mechanism whereby Lewis acid undergoes a counterion swap with the complex which favors isomerization as well as forming adducts with ancillary ligands, freeing coordination sites for internal alkene coordination polymerization.

Double hydroboration of dienes is the addition of a hydrogen and a boryl group to the two double bonds of a diene molecule and represents a straightforward and effective protocol to prepare synthetically versatile bis(boryl)alkanes, provided that this reaction occurs selectively. However, this reaction can potentially yield several isomeric organoboron products, and it still remains a challenge to control the regioselectivity of this reaction, which allows the selective production of a single organoboron product, in particular, for a broad scope of dienes. By employing a readily available cobalt catalyst, here we show that this double hydroboration yields synthetically useful gem-bis(boryl)alkanes with excellent regioselectivity. In addition, the scope of dienes for this reaction is broad and encompasses a wide range of conjugated and non-conjugated dienes. Furthermore, mechanistic studies indicate that this cobalt-catalyzed double hydroboration occurs through boryl-directed chain-walking hydroboration of alkenylboronates generated from anti-Markovnikov 1,2-hydroboration of 1,n-diene., Control of regioselectivity in the double hydroboration of dienes to obtain a single organoboron compound is a considerable synthetic challenge. Here, the authors show a cobalt-catalyzed chain-walking double hydroboration of 1,n-dienes to access gem-bis(boryl)alkanes with regioselective control.

This paper provides a guide to identify and understand the mechanistic origin of the catalytic activity and selectivity in the production of linear and branched polyethylene through a nickel hydride catalyst. Nickel active species were experimentally detected through ionization mass spectrometry experiments during ethylene polymerization from neutral diketiminate nickel pre-catalyst LNi(η3-allyl) activated with B(C6F5)3. Density functional theory (DFT) calculations were performed to investigate the competitiveness between linear and branched polymer formation in nickel hydride species, indicating that the branching degree of the obtained polyethylene was reduced by steric effects of the ligand at the nickel center, as well as by stabilization of intermolecular non-covalent interactions with the growing polymer chain at the secondary coordination sphere. The highest probability of branched-chain formation was 25% (at 343 K). Additionally, linear PE formation is attributed to an increased insertion rate (higher TOF) relative to the chain walking rate (lower TOF). This work could provide information on the rational design of similar metal hydride catalysts.

Thermal field-flow fractionation (ThFFF) was designed to investigate the retention behavior of a series of dendritic polyethylenes synthesized using a chain walking catalyst (cwPE) with variations ...

Recently developed chain walking (CW) catalysis is an elegant approach to produce materials with controllable structure and properties. However, there is still a lack in understanding of how the reaction mechanism influences the macromolecular structures. In this study, a series of dendritic polyethylenes (PE) synthesized by Pd-α-diimine-complex through CW catalysis (CWPE) is investigated by means of theory and experiment. Thereby, the exceptional ability of in situ tailoring polymer structure by varying synthesis parameters was exploited to tune the branching architecture, which allowed us to establish a precise relationship between synthesis, structure, and solution properties. The systematically produced polymers were characterized by state-of-the-art multidetector separation and neutron scattering experiments as well as atomic force microscopy to access molecular properties of CWPE. On a global scale, the CWPE appear in a worm-like conformation independently on the synthesis conditions. However, severe differences in their contraction factors suggested that CWPE differ substantially in topology. These observations were verified by NMR studies that showed that CWPE possess a constant total number of branches but varying branching distribution. Small angle neutron scattering experiments gave access to structural characteristics from global to segmental scale and revealed the unique heterogeneity of CWPE, which is predominantly based on differences in their dendritic side chains. The experimental data were compared to theoretical CW structures modeled with different reaction-to-walking probabilities. Simple theoretical arguments predict a crossover from dendritic to linear topologies yielding a structural range from purely linear to dendritic chain growth. Yet, comparison of theoretical and empirical scattering curves gave the first evidence that a transition state to worm-like topologies is actually experimentally accessible. This crossover regime is characterized by linear global features and dendritic local substructures contrary to randomly hyperbranched systems. Instead, the obtained CWPE systems have characteristics of disordered dendritic bottle brushes and can be adjusted by the walking rate/reaction probability of the catalyst.