Yasutomo Segawa

Synthesis of Extended π‐Systems through C–H Activation

Activation of aromatic CH bonds by a transition metal catalyst has received significant attention in the synthetic chemistry community. In recent years, rapid and site-selective extension of π-electron systems by C-H activation has emerged as an ideal methodology for preparing organic materials with extended π-systems. This Review focuses on recently reported π-extending C-H activation reactions directed toward new optoelectronic conjugated materials.

Synthesis of Cycloparaphenylenes and Related Carbon Nanorings: A Step toward the Controlled Synthesis of Carbon Nanotubes

Since their discovery in 1991, carbon nanotubes (CNTs) have attracted significant attention because of their remarkable mechanical, electronic, and optical properties. Structural uniformity of the CNT is critically important because the sidewall structures (armchair, zigzag, and chiral) determine many of the significant properties of CNTs. Ideally researchers would synthesize CNTs with a defined target sidewall structure and diameter, but the current synthetic methods, such as arc discharge and chemical vapor deposition, only provide CNTs as the mixtures of various structures. Purification of these mixtures does not allow researchers to isolate a structurally uniform CNT, which is the bottleneck for fundamental studies and advanced applications of these materials. Therefore, the selective and predictable synthesis of structurally uniform CNTs would represent a critical advance in both nanocarbon science and synthetic chemistry. This Account highlights our efforts toward the bottom-up synthesis of structurally uniform carbon nanotubes (CNTs). We envisioned a bottom-up synthesis of structurally uniform CNTs through a controlled growth process from a short carbon nanoring (template) that corresponds to the target structure of CNTs. Our simple retrosynthetic analysis led to the identification of cycloparaphenylenes (CPPs), acene-inserted CPPs, and cyclacenes as the shortest sidewall segments of armchair, chiral, and zigzag CNTs, respectively. With this overall picture in mind, we initiated our synthetic studies of aromatic rings/belts as an initial step toward structurally uniform CNTs in 2005. This research has led to (i) a general strategy for the synthesis of CPPs and related carbon nanorings using cyclohexane derivatives as a benzene-convertible L-shaped unit, (ii) a modular, size-selective, and scalable synthesis of [n]CPPs (a shortest segment of armchair CNTs), (iii) the X-ray crystal structure analysis of CPPs, (iv) the design and synthesis of acene-inserted CPPs as the shortest segment of chiral CNTs, and (v) the first synthesis of cyclo-1,4-naphthylene, a π-extended CPP. We believe this work will serve as important initial steps toward a controlled synthesis of CNTs.

Chemistry of Boryllithium: Synthesis, Structure, and Reactivity

A series of lithium salts of boryl anion, boryllithiums, were synthesized and characterized by NMR spectroscopy and crystallographic analysis. In addition to the parent boryllithium compound 35a, structural modification of boryllithium, using saturated C-C and benzannulated C=C backbones in the five-membered ring and mesityl groups on the nitrogen atoms, also allowed generation of the corresponding boryllithium. The solid state structures of boryllithium showed that the boron-lithium bond is polarized where the boron atom is anionic in all (35a x DME)(2), 35a x (THF)(2), 35b x (THF)(2), and 35c x (THF)(2) when compared to the structures of hydroborane 38a-c and optimized free boryl anion opt-46a-c. Dissolution of the isolated single crystals of (35a x DME)(2) and 35a x (THF)(2) in THF-d(8) showed that the boron-lithium bond remained in solution and free DME or THF molecules were observed. Temperature-dependent (11)B NMR chemical shift changes of 35a were observed in THF-d(8) or methylcyclohexane-d(14), suggesting a change of chemical shift anisotropy around the boron center. The HOMO of opt-35a x (THF)(2) had a lone pair character on the boron atom, as observed for phenyllithium, whereas the HOMO of hydroborane 38a corresponds to the pi-orbital of the boron-containing five-membered heterocycle. The polarity of the B-Li bond, estimated by AIM analysis, was similar to that of alkyllithium. Boryllithiums 35a and 35b behave as a base or a boron nucleophile in reaction with organic electrophiles via deprotonation, S(N)2-type substitution, halogen-metal exchange or electron-transfer, 1,2-addition to a carbonyl group, and S(N)Ar reaction. In the case of the reaction with CO(2), intramolecular cyclization followed by CO elimination from borylcarboxylate anion and subsequent protonation gave hydroxyboranes 64a and 64b. The characters of the carbonyl groups in the borylcarbonyl compounds 60a, 60b, 61, 62, and 63a, which were obtained from the reaction of boryllithiums 35a and 35b, were investigated by X-ray crystallography, IR, and (13)C NMR spectroscopy to show that the boryl substituent weakened the C=O bond when compared to carbon substituted analogues.

Concise Synthesis and Crystal Structure of [12]Cycloparaphenylene

bottom-up chemical synthesis of this simple molecular entity had been recognized as a Holy Grail in synthetic chemistry, three groups including our own have recently succeeded in synthesizing some [n]CPPs. Although these studies from the three research groups established the synthetic viability of the long-awaited CPPs, important issues remain unresolved (Scheme 1). For example, any synthetic route must be more concise, cost-effective, and scalable to provide CPP in useful quantities and to ensure that this interesting molecular entity is studied further. In addition, the molecular structure of CPP must be concretely validated by X-ray crystallographic analysis. We herein report a concise nickel-based synthesis of [12]CPP and the first X-ray crystal structure of [12]CPP. Some of the key features of the previous methods of making CPPs are summarized in Scheme 2. Both the group of Bertozzi and ours utilized the palladium-catalyzed Suzuki–Miyaura coupling of terphenyl-convertible bent

A Modular and Size‐Selective Synthesis of [n]Cycloparaphenylenes: A Step toward the Selective Synthesis of [n,n] Single‐Walled Carbon Nanotubes

the groups led by Bertozzi, Itami, 7] and Yamago have finally accomplished the bottom-up organic synthesis of some [n]CPPs (n = 8, 9, 12, 18). Although several possible routes toward CPP structures have been identified in these studies, a uniform strategy allowing the flexible and size-selective synthesis of a range of [n]CPPs has yet to be developed. Devising such a strategy is important in view of the expectation that CPP could serve as a precursor or seed in the preparation of structurally uniform armchair single-walled carbon nanotubes (SWNTs) (Scheme 1). 9] As proposed and demonstrated by others, the amplification growth strategy using a relatively short hydrocarbon template such as CPP holds the promise of a long-awaited selective synthesis of SWNTs. In such a strategy, a modular and size-selective synthesis of [n]CPPs would be critically important in providing [n,n]SWNTs in a controlled and selective fashion. We now describe a modular and size-selective synthetic approach to [n]CPPs (n 14) and report the synthesis of [14]-, [15]-, and [16]CPP as a proof-of-principle of our new strategy. Our CPP synthesis is very flexible, assembling bent and linear building blocks in a controlled and programmable manner. In essence, we previously synthesized [12]CPP in a 3+3+3+3 mode using a terphenyl-equivalent L-shaped diphenylcyclohexane unit; Pd-catalyzed stepwise formation of a “box” (3+3+3 and then 9+3), followed by aromatization (Scheme 2). By strategically varying the number of bent

Syntheses of PBP Pincer Iridium Complexes: A Supporting Boryl Ligand

We synthesized a PBP pincer ligand precursor 2 and demonstrated its complexation with iridium(I) to afford the coordinatively unsaturated [PBP](hydrido)chloroiridium complex 3 via B-H oxidative addition. The reaction of 3 with carbon monoxide produced [PBP](hydrido)chloro(carbonyl)iridium 7. The longer Ir-Cl bond length of 7 than that of 8 revealed a stronger sigma-donor ability of the PBP ligand than that of PCP. Complex 3 was also converted to [PBP](ethylene)iridium(I) complex 9 by the reaction with LiTMP under an ethylene atmosphere.

Synthesis and properties of [9]cyclo-1,4-naphthylene: a π-extended carbon nanoring.

The first synthesis of a π-extended carbon nanoring, [9]cyclo-1,4-naphthylene ([9]CN), has been achieved. Careful structure-property analyses uncovered a number of unique features of [9]CN that are quite different from those of [9]CPP, a simple carbon nanoring.

Direct arylation of polycyclic aromatic hydrocarbons through palladium catalysis.

We have discovered that the combination of Pd(OAc)(2)/o-chloranil can catalyze the direct C-H bond arylation of polycyclic aromatic hydrocarbons (PAHs) with arylboroxins that occurs selectively at the K-region. The sequential integration of Pd-catalyzed direct arylation of PAHs and FeCl(3)-mediated cyclodehydrogenation is effective in rapidly extending a parent PAH π-system with high directionality.

Synthesis and racemization process of chiral carbon nanorings: a step toward the chemical synthesis of chiral carbon nanotubes.

A simple and realistic model for the shortest sidewall segments of chiral single-walled carbon nanotubes (SWNTs) has been designed, and one of the chiral carbon nanorings, cyclo[13]paraphenylene-2,6-naphthylene ([13]CPPN, 1) has been successfully synthesized. DFT calculations reveal that the racemization energy of 1 is 8.4 kcal·mol(-1). In addition, some important energetic values, such as racemization barriers and strain energies, of other chiral carbon nanorings have been systematically estimated for future molecular design.

Synthesis, Structures, and Properties of π-Extended Double Helicene: A Combination of Planar and Nonplanar π-Systems

The synthesis, structures, and properties of a π-extended double helicene 1 are described. This double helicene 1 was synthesized by a four-fold oxidative C-H biphenylation of naphthalene followed by the Scholl reaction or via five steps including the Suzuki-Miyaura cross-coupling reaction and the Scholl reaction. Due to the two helical substructures, 1 has three isomers, i.e., two enantiomers in a twisted form [(P,P) and (M,M)] and one diastereoisomer in a meso form. X-ray crystallographic analysis of the twisted isomers (twisted-1) revealed a tightly offset packing pattern of (P,P)- and (M,M)-twisted isomers, affording a three-dimensional lamellar stacking structure. A high isomerization barrier (43.5 kcal mol(-1)) and the relative thermal stability of twisted-1 isomer over meso-1 by 0.9 kcal mol(-1) were estimated by DFT calculations. The three isomers were successfully separated by chiral HPLC and characterized by circular dichroism spectroscopy as well as by TD-DFT studies. Electronic state variation resulting from the molecular geometry difference between the two diastereoisomers (twisted-1 and meso-1) was observed by UV-vis absorption and fluorescence spectra.