Achiral Bis Research Articles

"Sergeants-and-soldiers" principle in the synthesis of intrinsically chiral Au13 clusters.

Surface ligand modification on atomically precise metal clusters is one of the important strategies not only to stabilize monodisperse clusters, but also to derive unique optical and electronic properties. The chiral coordination of surface ligands on clusters controls the global chirality in clusters giving rise to unambiguous optical activity including circular dichroism (CD) and circularly polarized luminescence (CPL). Stereoselective synthesis of intrinsically chiral clusters has been achieved by the use of chiral ligands stabilizing one-handed clusters selectively. Herein, we investigate the effect of chiral ligand coordination on the deracemization of intrinsically chiral Au13 superatom clusters. The mixture of achiral bis(diphenylphosphino)ethane (DPPE) and chiral (R,R)-1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (R-DIPAMP) led to the formation of a mixture of [Au13(R-DIPAMP)x(DPPE)5-xCl2]3+ clusters with varied x-values (x = 0-5). Reverse phase HPLC successfully fractionalized the mixture into solutions composed of single component Au13 clusters depending on the x-values. The separated Au13 clusters afforded similar optical activity to that of [Au13(R-DIPAMP)5Cl2]3+ in the CD study regardless of x-values (x = 1-4). The DFT calculation supports that the coordination of a single DIPAM ligand is enough to bias the twisting direction in the Au13 superatom with dictating the tortional orientation of other four DPPE ligands. The emergence of the "sergeants-and-soldiers principle", wherein a small number of chiral ligands determine the chiral orientation of other achiral ligands, is thus demonstrated in the synthesis of intrinsically chiral Au13 clusters.

Synthesis of Single‐Handed Helical Spiro‐Conjugated Ladder Polymers through Quantitative and Chemoselective Cyclizations**

AbstractWe report the unprecedented synthesis of one‐handed helical spiro‐conjugated ladder polymers with well‐defined primary and secondary structures, in which the spiro‐linked dibenzo[a,h]anthracene fluorophores are arranged in a one‐handed twisting direction, through quantitative and chemoselective acid‐promoted intramolecular cyclizations of random‐coil precursor polymers composed of chiral 1,1′‐spirobiindane and achiral bis[2‐(4‐alkoxyphenyl)ethynyl]phenylene units. Intense circular dichroism (CD) and circularly polarized luminescence (CPL) were observed, whereas the precursor polymers exhibited negligible CD and CPL activities. The introduction of 2,6‐dimethyl substituents on the 4‐alkoxyphenylethynyl pendants is of key importance for this simple, quantitative, and chemoselective cyclization. This strategy is applicable to the defect‐free precise synthesis of other varieties of fully π‐conjugated molecules and coplanar ladder polymers that have not been achieved before.

Synthesis of Single-Handed Helical Spiro-Conjugated Ladder Polymers through Quantitative and Chemoselective Cyclizations*.

We report the unprecedented synthesis of one-handed helical spiro-conjugated ladder polymers with well-defined primary and secondary structures, in which the spiro-linked dibenzo[a,h]anthracene fluorophores are arranged in a one-handed twisting direction, through quantitative and chemoselective acid-promoted intramolecular cyclizations of random-coil precursor polymers composed of chiral 1,1'-spirobiindane and achiral bis[2-(4-alkoxyphenyl)ethynyl]phenylene units. Intense circular dichroism (CD) and circularly polarized luminescence (CPL) were observed, whereas the precursor polymers exhibited negligible CD and CPL activities. The introduction of 2,6-dimethyl substituents on the 4-alkoxyphenylethynyl pendants is of key importance for this simple, quantitative, and chemoselective cyclization. This strategy is applicable to the defect-free precise synthesis of other varieties of fully π-conjugated molecules and coplanar ladder polymers that have not been achieved before.

A Highly Luminescent Chiral Tetrahedral Eu4L4(L')4 Cage: Chirality Induction, Chirality Memory, and Circularly Polarized Luminescence.

Chiral lanthanide cages with circularly polarized luminescence (CPL) properties have found potential application in enantioselective guest recognition and sensing. However, it still remains a big challenge to develop a simple and robust method for the diastereoselective assembly of homochiral lanthanide cages in view of the large lability of the Ln(III) ions. Herein, we report the first example of the formation of a enantiopure lanthanide tetrahedral cage via a chiral ancillary ligand induction strategy. One such cage, (Eu4L4)(R/S-BINAPO)4, is assembled by four achiral C3-symmeric tris(β-diketones) (4,4',4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)triphenylamine, L) as faces, four Eu(III) ions as vertices and four chiral R-/S-bis(diphenylphosphoryl)-1,1'-binaphthyl (R/S-BINAPO) as ancillary ligands. X-ray crystallography and NMR and CD spectra confirm the formation of a pair of enantiopure chiral topological tetrahedral cages, (Eu4L4)(R-BINAPO)4 and (Eu4L4)(S-BINAPO)4 (ΔΔΔΔ-1 and ΛΛΛΛ-1). As expected, the tetrahedral cages present strong CPL with |glum| values up to 0.20, while they unexpectedly give ultrahigh luminescent quantum yields (QYs) of up to 81%, the highest value reported in chiral Ln(III) complexes. More impressively, the chiral memory effect for a lanthanide-based assembly is observed for the first time. The chirality of the original cage 1 framework is retained after R/S-BINAPO is replaced by the achiral bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), and thus another pair of enantiopure Eu(III) tetrahedral cages, ΔΔΔΔ- and ΛΛΛΛ-[(Eu4L4)(DPEPO)4] (ΔΔΔΔ-2 and ΛΛΛΛ-2), have been isolated. Encouragingly, cage 2 also presents an impressive luminescence quantum yield (QY = 68%) and intense CPL (|glum| = 0.11). This study offers a simple and low-cost synthesis strategy for the preparation of lanthanide cages with CPL properties.

Bis-Porphyrin Structural Motiff for Chirality and Molecular Sensing

Bis-porphyrin structures are widely used as model systems to mimic various natural processes and have numerous practical applications in the research and technoligical fields such as polymer and nano science, light harvesting and nonlinear optics, chemical sensors and catalysis, molecular and chiral recognition, various supramolecular and chiroptical devices, chirogenesis and absolute configuration determination. Several years ago, we have discovered that a simple ethane-bridged bis-porphyrin structural motif (M = Zn, Mg, Cu, Co, 2H), can be effectively served for different application purposes owing to the specific molecular and supramolecular functionalities. In particular, the unique functional property of this bis-porphyrin host is based upon the structural semi-flexibility of covalent linkage between two porphyrin unitsresulting in the environmentally assisted syn-anti conformational switching and tweezer formation depending upon the guest structure, which can be effectively employed in different sensing areas, such as chirogenic probes, chiral recognitions, and chemical sensors .1-13 Further developments and prospects toward new chiral and achiral bis- and multi porphyrin systems on the basis of heterometallic bis- and multi-porphyrin structures will be discussed. Borovkov, Symmetry 2014, 6, 256. Borovkov, Symmetry 2010, 2, 184. Borovkov, Y. Inoue, Eur. J. Org. Chem. 2009, 189. A. Hembury, V. V. Borovkov, Y. Inoue, Chem. Rev. 2008, 108, 1. V. Borovkov, Y. Inoue, Top. Curr. Chem. 2006, 265, 89. V. Borovkov, G. A. Hembury, Y. Inoue, Acc. Chem. Res. 2004, 37, 449.Giancane, V. Borovkov, Y. Inoue, L. Valli, J. Colloid Interface Sci. 2012, 385, 282.Giancane, V. Borovkov, Y. Inoue, S. Conoci, L. Valli,Soft Matter 2013, 9, 2302.Bettini, E. Maglie, R. Pagano, V. Borovkov, Y. Inoue, L. Valli, G. Giancane, Beilstein J. Nanotechnol. 2015, 6, 2154.Colombelli, M.G. Manera, V. Borovkov, G. Giancane, L. Valli, R. Rella, Sensor Actuat. B-Chem. 2017, 246, 1039. Buccolieri, D. Manno, A. Serra, A. Santino, M. Hasan, V. Borovkov, G. Giancane,Sensor Actuat. B-Chem. 2018, 257, 685.Buccolieri, M. Hasan, S. Bettini, V. Bonfrate, L. Salvatore, A.Santino, V. Borovkov, G.,Giancane, Anal. Chem. 2018, 90, 6952.Bettini, R. Pagano, V. Borovkov, G. Giancane , L. Valli, J. Colloid Interface Sci. 2019, 533, 762-770.

Chiral Microneedles from an Achiral Bis(boron dipyrromethene): Spontaneous Mirror Symmetry Breaking Leading to a Promising Photoluminescent Organic Material.

Supramolecular self-assembly of a highly flexible and achiral meso bis(boron dipyrromethene) [bis(BODIPY)] dye straightforwardly yields fluorescent microfibers, exhibiting an intriguing anisotropic photonic behavior. This performance includes the generation of chiroptical activity owing to spontaneous mirror symmetry breaking (SMSB). Repetition of several self-assembly experiments demonstrates that the involved SMSB is not stochastic but quasi deterministic in the direction of the induced chiral asymmetry. The origin of these intriguing (chiro)photonic properties is revealed by fluorescent microspectroscopy studies of individual micrometric objects, combined with X-ray diffraction elucidation of microcrystals. Such a study demonstrates that J-like excitonic coupling between bis(BODIPY) units plays a fundamental role in their supramolecular organization, leading to axial chirality. Interestingly, the photonic behavior of the obtained fibers is ruled by inherent nonradiative pathways from the involved push-pull chromophores, and mainly by the complex excitonic interactions induced by their anisotropic supramolecular organization.

Controlling Supramolecular Chirality of Two-Component Hydrogels by J- and H-Aggregation of Building Blocks.

While manipulating the helicity of nanostructures is a challenging task, it attracts great research interest on account of its crucial role in better understanding the formation mechanisms of helical systems. For the supramolecular chirality in self-assembly systems, one challenge is how to understand the origin of supramolecular chirality and inherent helicity information on nanostructures regulated by functionality-oriented stacking modes (such as J- and H-aggregation) of building blocks. Herein, two-component hydrogels were prepared by phenylalanine-based enantiomers and achiral bis(pyridinyl) derivatives, where helical nanofibers with inverse handedness as well as controllable helical pitch and diameter were readily obtained through stoichiometric coassembly of these building blocks. The helix inversion was achieved by the transition between the J- and H-aggregation of bis(pyridinyl) derivatives, which was collectively confirmed by circular dichroism, scanning electron microscopy, Fourier transform infrared spectroscopy, and single X-ray crystallography. Interestingly, the helical coassemblies with opposite handedness could be obtained not only from the enantiomeric building blocks but also from the chiral monomers with the same configurational chirality by exchanging achiral additives. This work provides insight into the origin and helicity inversion of supramolecular chirality in molecular self-assembly systems and may shine light on the precise fabrication of chiral nanostructures for potential applications in smart display devices, optoelectronics, and biological systems.

Inversion of the Supramolecular Chirality of Nanofibrous Structures through Co‐Assembly with Achiral Molecules

AbstractTo understand the behavior of chiral nanostructures, it is of critical importance to study how achiral molecules regulate the chirality of such nanostructures and what the main driving forces for the regulation processes are. In this work, the supramolecular chirality of helical nanofibers consisting of phenylalanine‐based enantiomers is inverted by achiral bis(pyridinyl) derivatives through co‐assembly. This inversion is mainly mediated by intermolecular hydrogen bonding interactions between the achiral additives and the chiral molecules, which may induce stereoselective interactions and different reorientations for the assembled molecules, as confirmed by calculations. This work not only exemplifies a feasible method to invert the helicity of chiral nanostructures by the addition of achiral molecules, but also provides a method to explore their functions in environments where chiral and achiral molecules are in close proximity.

Inversion of the Supramolecular Chirality of Nanofibrous Structures through Co-Assembly with Achiral Molecules.

To understand the behavior of chiral nanostructures, it is of critical importance to study how achiral molecules regulate the chirality of such nanostructures and what the main driving forces for the regulation processes are. In this work, the supramolecular chirality of helical nanofibers consisting of phenylalanine-based enantiomers is inverted by achiral bis(pyridinyl) derivatives through co-assembly. This inversion is mainly mediated by intermolecular hydrogen bonding interactions between the achiral additives and the chiral molecules, which may induce stereoselective interactions and different reorientations for the assembled molecules, as confirmed by calculations. This work not only exemplifies a feasible method to invert the helicity of chiral nanostructures by the addition of achiral molecules, but also provides a method to explore their functions in environments where chiral and achiral molecules are in close proximity.

Preparation of chiral imidazolin-2-imine ligands and their application in ruthenium-catalyzed transfer hydrogenation

2-Chloro-1,3-diisopropyl-4,5-dimethylimidazolium tetrafluoroborate (1) serves as a convenient starting material for the preparation of mono- and bis(imidazolin-2-imine) ligands. Thus, the reaction of two equivalents of 1 with 1,2-ethylenediamine in the presence of potassium fluoride afforded the bis(2-aminoimidazolium) salt [BLiPrH2][BF4]2 (2), from which the achiral bis(imidazolin-2-imine) ligand N,N′-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,2-ethanediamine (BLiPr) can be obtained by deprotonation. Likewise, the reaction of 1 with (1R,2R)-(−)-1,2-diaminocyclohexane (DACH) gave [DACH(ImiPrH)2][BF4]2 (3) and its deprotonation the chiral, C2-symmetric diimine DACH(ImiPr)2 (4). Under similar conditions, chiral, C1-symmetric mono(imidazolin-2-imines) were obtained from the reaction of 1 with one equivalent of (1R,2R)-(−)-1,2-diaminocyclohexane (DACH) or (1S,2S)-(−)-1,2-diphenylethylenediamine (DPEN), which afforded the 2-aminoimidazolium salts [DACH(ImiPrH)NH2][BF4] (5) and [DPEN(ImiPrH)NH2][BF4] (6), respectively. The reaction of 4 with [(C6H6)RuCl2]2 gave ruthenium complex [(C6H6)Ru{DACH(ImiPr)2}]Cl2, [7]Cl2, which was treated with KPF6 to form [7][PF6]2. The ligand precursors 5 and 6 were deprotonated in the presence of [(C6H6)RuCl2]2, which resulted in the formation of complexes [(C6H6)Ru{DACH(ImiPr)NH2}Cl]Cl [8]Cl and [(C6H6)Ru{DPEN(ImiPr)NH2}Cl]Cl [9]Cl. Complexes [7][PF6]2, [8]Cl and [9]Cl were investigated for their ability to catalyze the transfer hydrogenation of acetophenone in isopropanol. Complex [8]Cl proved to be the most active system, while complex [9]Cl produced the highest enantioselectivity, albeit of only 27% ee. The molecular structures of [7][(C6H6)RuCl3]2·CH2Cl2, formed as a side product, and of [8]Cl·acetone were determined by X-ray diffraction analyses.

Helix‐Sense‐Selective Polymerization of Achiral Bis(hydroxymethyl)phenylacetylenes Bearing Alkyl Groups of Different Lengths

Abstract4‐Alkyloxy‐3,5‐bis(hydroxymethyl)phenylacetylenes with eight types of alkyl groups were synthesized and polymerized with a chiral catalytic system. We found that the length of the alkyl groups played a very important role in achieving helix‐sense‐selective polymerization. Five helix‐sense‐selective polymerizations were achieved resulting in polymers with alkyl groups whose chain length was longer than six. We think that the longer‐chain alkyl groups prevented the polymers from becoming insoluble by forming intermolecular hydrogen bonds between the hydroxyl groups, and stabilized their one‐handed helical structure by promoting the formation of intramolecular hydrogen bonds.magnified image

Asymmetric Transformation of a Double-Stranded, Dicopper(I) Helicate Containing Achiral Bis(bidentate) Schiff Bases

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionORIGINAL ARTICLEThis notice is a correctionAsymmetric Transformation of a Double-Stranded, Dicopper(I) Helicate Containing Achiral Bis(bidentate) Schiff BasesNicolle C. Habermehl, Patricia M. Angus, Nathan L. Kilah, Lasse Norén, A. David Rae, Anthony C. Willis, and S. Bruce WildCite this: Inorg. Chem. 2006, 45, 22, 9146Publication Date (Web):September 29, 2006Publication History Published online29 September 2006Published inissue 30 October 2006https://doi.org/10.1021/ic0680009Copyright © 2006 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views446Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (11 KB) Get e-Alerts Get e-Alerts

Synthesis of Type II β-Turn Surrogate Dipeptides Based on syn-α-Amino-α,β-dialkyl-β-lactams

The achiral bis(trimethylsilyl)methyl group acts as an efficient stereochemical determinant of the alpha-alkylation reaction in beta-branched alpha-phenyloxazolidinyl- or alpha-diphenyloxazolidinyl-beta-lactams and provides the first stereocontrolled access to syn-alpha-amino-alpha,beta-dialkyl(aryl)-beta-lactams. These products are readily transformed into type II beta-turn mimetic surrogates 2B. [reaction: see text]

Rationalization of supramolecular chirality in a bisporphyrin system.

A sign of the times: A 1:1 tweezer complex consisting of an achiral bis(zinc porphyrin) and (R,R)-1,2-diaminocyclohexane has been characterized by X-ray crystallographic analysis (see picture, Zn red, N blue). This has enabled a full and unambiguous rationalization of the highly efficient transfer of chirality information from an optically active guest to an achiral host in a supramolecular system based on a bisporphyrin to be carried out.

Chiral and achiral bis(2‐oxazolinylphenolato)nickel(II) complexes—synthesis, crystal structure, and catalytic properties

AbstractA series of chiral and achiral bis(2‐oxazolinylphenolato)nickel@) complexes 2 were synthesized by reactions of various 2‐(4, 5dihydro‐2‐oxazolyl)phenol derivatives with nickel chloride hexahydrate. The molecular structure of complex 2a was determined by X‐ray single crystal diffraction. The crystal of complex 2a was monoclinic, space group P21 with cell dimension of a= 1.1121(4) nm, b=0.9472(3) nm, c=1.4113(5) nm, α=γ=90°,β=91. 450(6)°, V=1.4861(8) nm3, Z=2, and μ=0.693 mm−1. In the solid state, the nickel(II) ion was in a square‐planar coordination geometry. The catalytic activities of complexes 2 in Baeyer‐Villiger reaction with molecular oxygen were investigated.

The origin of solvent-controlled supramolecular chirality switching in a bis(zinc porphyrin) system.

Inducing chirality: The supramolecular interaction of achiral bis(zinc porphyrin) with enantiopure amino acid derivatives in different solvents results in chirality induction. The sign and degree of the circular dichroims is controlled by the solvent polarity (see picture).

Increased enantioselectivity in the addition of diethylzinc to benzaldehyde by the use of chiral ligands containing the alpha-phenylethylamino group in combination with achiral ligands.

Chiral ligands (S,S)-1, (S,S)-2, (S,S)-3, (S)-4, (S)-5, (S,S)-6, (S,S)-7, and (S,S)-8 turned out to be effective promoters in the enantioselective addition of diethylzinc to benzaldehyde. Interestingly, diamine (S,S)-3 and amino alcohols (S)-5 and (S,S)-7 induce the preferential formation of carbinol (R)-10 (unlike stereoinduction) whereas amido analogues (S,S)-2, (S)-4, and (S,S)-6 favor (S)-10 (like stereoinduction). Molecular modeling at the semiempirical PM3 level provided a reasonable interpretation based on conformational effects in the corresponding transition structures. Combinations of chiral ligands 1-8 with an achiral, flexible ligand (9) gave rise to an activated catalytic system that resulted in faster and higher yielding reactions. Furthermore, substantial increases in the observed enantiomeric excesses of product 10 confirmed the relevant role of achiral bis(sulfonamide) 9 as activator and "chiral environment amplifier".

Supramolecular chirogenesis in bis(zinc porphyrin): An absolute configuration probe highly sensitive to guest structure

The role of the ligand's structure and absolute configuration in the supramolecular chirality induction in achiral bis(zinc porphyrin) has been studied. The amines with bulkier substituents resulted in stronger CD signals due to increased helical displacement in the anti conformer. All the amines with an R absolute configuration gave a negative first Cotton effect and positive second Cotton effect, while the ligands with an S absolute configuration produced CD signals with opposite signs due to formation of the left- and right-handed screw diastereomers, respectively.

Enantioselective catalysis: Part 114. Chirostructural analysis of bis(diphenylphosphanyl)ethane transition metal chelates

Transition metal complexes of bis(diphenylphosphanyl)ethane type ligands play an important role in asymmetric catalysis. The four phenyl substituents form a chiral array responsible for the high optical yields achieved with these ligands. In this paper we present an analysis of the phenyl ring orientations based on a search in the Cambridge Structural Database (CSD). The phenyl arrangements are not only subdivided into the well known face and edge exposed types, but they are additionally distinguished by the sign of the torsion angle M–P–C ipso –C ortho according to their chirality into face-P, face-M, edge-P, and edge-M. This approach allows a more differentiated examination. We found, that the phenyl rings prefer certain orientations within a small range depending on their axial or equatorial position and the ligand chirality. A comparison of these results with those of an analysis of achiral bis(diphenylphosphanyl)ethane complexes shows, that the substituents at the ligand backbone of the chiral phosphines reinforce the typical phenyl ring orientation in optically active phosphine complexes.

Multiple Cyclopropanations of C70. Synthesis and characterization of bis‐, tris‐, and tetrakis‐adducts and chiroptical properties of bis‐adducts with chiral addends, including a recommendation for the configurational description of fullerene derivatives with a chiral addition pattern

AbstractThe regioselectivity of multiple cyclopropanations of C70 with 2‐bromopropanedioates in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as base (Bingel reaction) was investigated in a systematic study. Bisadduct formation occurred preferentially at the 66 bonds formed by the most pyramidalized sp2‐C‐atoms at the two opposite poles of the fullerene and, in the reaction with achiral bis[(ethoxycarbonyl)methyl]2‐bromopropanedioate (13a), yielded three constitutionally isomeric bis(methano)fullerenes (Scheme 2). Two of them, C2‐symmetrical (±)‐1 and (±)‐2, are chiral; a fact which had not been considered in previous investigations. Formation of the third, C2v‐symmetrical isomer 3 was observed for the first time. Configurational descriptions for fullerene derivatives which possess a chiral chromophore as a result of specific functionalization patterns are proposed. Cyclopropanations of C70 with optically active bis[(S)‐1‐phenylbutyl] 2‐bromopropanedioate (13b) yielded five optically active, C2‐symmetrical bis‐adducts 7–11 which could be separated by preparative HPLC and fully characterized (Scheme 3, Fig.4). Compounds 7/8 and 9/10 represent two constitutionally isomeric pairs of diastereoisomers, and their circular dichroism (CD) spectra show pronounced Cotton effects mainly due to strong chiroptical contributions from the chirally functionalized fullerene chromophores (Fig.7). Since the addition patterns on the fullerene surface in each pair of diastereoisomers have an enantiomeric relationship, their CD spectra closely resemble those expected for two enantiomers. In the third constitutional isomer 11, the addition pattern on the fullerene surface is C2v‐symmetrical, and optical activity only results from the chiral addends. Its CD spectrum shows weak Cotton effects mainly from induced circular dichroism originating from the perturbation of the achiral fullerene chromophore by the attached chiral addends. Addition of diethyl 2‐bromopropanedioate (2 equiv.) to the C2‐symmetrical racemic bis‐adduct (±)‐2 yielded a mixture of tris‐adducts and one major, C2‐symmetrical tetrakis‐adduct (±)‐4 which was isolated in pure form (Scheme 4). Starting from the achiral C2v‐symmetrical bis‐adduct 3, one single Cs‐symmetrical tris‐(5) and one C2v‐symmetrical tetrakis‐adduct (6) were obtained as major products which were isolated and fully characterized (Scheme 5). The regioselectivity for introduction of a second addend in the same hemisphere of C70 is high and resembles the preferred pattern of bis‐addition seen in the functionalization of C60.