DOI: 10.1002/cptc.

201900068 Minireviews
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Enantioselective Photochromism under Circularly Polarized
5 Light
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7 P. K Hashim[a] and Nobuyuki Tamaoki*[b]
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10 The introduction of asymmetry into molecular systems by contribute to the enhancement of spectral characteristics,
11 external chiral stimuli greatly contributes to our understanding which is highly desirable for the experimental observation of
12 of the intriguing homochirality which exists in biomolecules. CPL-based enantioselective reactions. In this Minireview, CPL-
13 Circularly polarized light (CPL) is a well-known chiral physical directed enantioselective photochromism, with an emphasis on
14 force (right- or left-handed), which can influence the enantio- several azobenzene derivatives, will be discussed. We briefly
15 meric equilibrium of racemic chiral compounds via preferential discuss the recent examples of chiral amplification methods
16 interaction with one of the enantiomers. As a light absorption that utilize CPL chiral forces along with a short perspective for
17 moiety in the chiral system, photochromic molecules best future directions.
18
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20 1. Introduction lecular homochirality.[8] Continuous exposure of amino acids
21 and sugars under CPL can generate biased chirality in small
22 Enantiomers of a chiral molecule possess two chemically excess, which then undergoes amplification process to enrich
23 identical structures with opposite spatial orientations that are single-handed chiral structures.[9] Studies focusing the induction
24 non-superimposable mirror images.[1] In the absence of external of chirality in model organic compounds surely contribute to
25 chiral influences, chiral molecule is a racemic mixture with equal better understand the plausible origin of single handed
26 numbers of constituent enantiomers. However, chiral environ- chirality of biomolecules.[10] In addition, photochromic systems
27 ments produced either by chemical reactions or physical forces and their reversible switching of molecular chirality by CPL
28 can potentially affect the equilibrium of the enantiomers irradiation has the potential to use in optical memory devices
29 leading to selective enrichment of one of the enantiomers with as a data storage material.[11] Experimentally, the biased optical
30 respect to the other.[2] In the case of biomolecules, L-amino rotation can be evident from their typical circular dichroism
31 acids and D-glucose, the enantiomeric enrichment (ee) is (CD) profile. For a chiral molecule capable of absorbing
32 appeared to be near maximum and only one enantiomer is ultraviolet (UV) or visible light, in principle, it is possible to
33 thus available in nature.[3] Of note, the homochirality of enrich one enantiomer from a racemic mixture by CPL
34 monomer biomolecules is a decisive prerequisite that governs irradiation. This enrichment of enantiomers takes place via
35 the spatial conformations when assembled into functioning three different mechanisms namely photodestruction, photo-
36 polymer such as polypeptides or nucleic acids. However, how resolution, or absolute asymmetric synthesis.[7] Photodestruc-
37 the biomolecules achieved asymmetric imbalance at the early tion by CPL irradiation stands for the preferential consumption
38 stage of evolution is still a scientific mystery, although several of one of the enantiomers of a racemic substrate causing the
39 theories and experimental evidences are reported.[4–6] Several enrichment of the other unreacted enantiomer.[12] In order to
40 physical forces such as linearly polarized light (LPL), left or expect ee by photodestruction method, enantiomers of a
41 right- handed circularly polarized light (l- or r-CPL), static racemic substrate should not interconvert under photochem-
42 magnetic field and magnetic field parallel to an electric field ical conditions.[13] In photoresolution, the starting compound is
43 has been tested to induce chirality in molecular system, but usually a chiral molecule with equal amount of enantiomers,
44 only CPL functioned as true source of chiral physical force that and upon photoirradiation enantioselective photochemical
45 produces detectable molecular chirality.[7] Additionally, consid- conversion produces one enantiomer in slight excess to its
46 erable amount of CPL has been detected in extraterrestrial mirror-image counterpart. Importantly photoresolution is a
47 region thereby depicting one plausible explanation of biomo- reversible process and can produce mirror-image enantiomers
48 from the same chiral molecule repeatedly by switching the
49 [a] Dr. P. K Hashim
handedness of chiral sources, i. e. l- or r-CPL.[14,15] Whereas in
50 Chemistry and Biotechnology absolute asymmetric photosynthesis, optically active com-
51 The University of Tokyo pound is selectively enriched directly from a prochiral material,
7-3-1 Hongo, Bunkyo Ku, Tokyo 113 8656 (Japan)
52 [b] Prof. Dr. N. Tamaoki
and the process generally occur irreversibly. However, rever-
53 Research Institute for Electronic Science sible asymmetric synthesis is also possible especially in the case
54 Hokkaido University, N20, W10 of prochiral molecules consisting photochromic moieties.[16,17]
Sapporo, Hokkaido 001-0020 (Japan)
55 E-mail: tamaoki@es.hokudai.ac.jp
Here, a single CPL irradiation can cause both chirality induction
56 An invited contribution to a Special Issue on Photoresponsive Molecular as well as enantiomeric enrichment in the same molecule,
57 Switches and Machines which may occur simultaneously or by step-wise manner.

ChemPhotoChem 2019, 3, 347 – 355 347 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Minireviews
1 Enantioselective synthesis of polymers by CPL irradiations is molecule (Figure 1a). Accordingly, CD spectral characteristics
2 also possible, where the preferential interaction of l- or r-CPL comparable with the CD spectra of pure enantiomers were
3 with the polymerizing moiety produce polymers with biased reversed upon successive irradiation with l-and r-CPL at
4 chirality.[18] In this minireview, we discuss recent progress of 313 nm. Although the magnitude of switching between P and
5 CPL induced chirality induction in photochromic systems with M helices at PSS was only 0.07 %, successive irradiations by l-
6 the emphasis on azobenzene derivatives. Photoresolution and r-CPL gave reproducible CD curves and the effect of
7 process of mono- or bicyclic azobenzene systems as well as chirality switch was further demonstrated by using as dopants
8 asymmetric synthesis of an azobenzene dimer is presented. In to modulate macroscopic chirality in liquid crystals. Schuster
9 the final section we briefly discuss the various amplification et al. reported an axially chiral cycloalkane that undergoes fast
10 methods studied, including those of non-photochromic sys- racemization by rotation about the double bond at excited
11 tems, where the enantiomeric excess and subsequent amplifi- state upon photoirradiation at 313 nm.[20] Consequently, the
12 cation were produced by CPL chiral stimuli. irradiation of racemic compound with CPL resulted the partial
13 resolution with an enantiomeric excess of 1.6 % (g313 = 0.0502,
14 eemax = 2.5 %), however the dynamic switching of partial enrich-
15 2. CPL-Induced Photoresolution ment was not studied. Later the same group synthesized axially
16 chiral bicyclic ketones 2 with relatively rigid bicycle[3,3,0]octane
17 Partial photoresolution by CPL irradiation involves selective skeleton and demonstrated reversible photoderacemization
18 enantio-differentiating photochemical reaction in a reversible upon successive irradiation of 2 with l-and r-CPL (Figure 1b).[21]
19 manner from a racemate in which l- or r-CPL produces excess Similarly, Inoue et al. achieved enantiodifferentiating photo-
20 of the R or S enantiomer. As a theoretical measure of enantio- isomerization of (E)-cyclooctene 3 at electronic excited state by
21 selectivity, Kuhn anisotropy factor g is often used that can be the CPL irradiation (Figure 1c).[22] The key in their design was to
22 defined as the ratio of molar circular dichroism (Δɛ) of a pure use a helical undulator as a source of monochromatic CPL in
23 enantiomer and extinction coefficient (Δɛ/ɛ).[19] Δɛ is the which the photoisomerizations lead to the simultaneous
24 difference in molar extinction coefficients (ɛ), which is calcu- conversion of both geometry and chirality of the molecule. CD
25 lated from the absorption and circular dichroism spectra of spectra obtained after irradiation with l- and r- CPL gave
26 pure enantiomers. Taking half of the g factor, enantiomeric opposite optical rotations, however no detectable optical
27 excess in the photostationary state (eePSS) can also be predicted activity observed upon LPL irradiation.
28 and most of the cases ee value of less than 1 % is expected
29 from the CPL photoresolution. One of the conditions to observe
30 photoresolution by CPL is the interconversion of enantiomers, 2.1. Photoresolution of Bicyclic Planar Chiral Molecules
31 which is possible either at ground state of a chiral molecule or
32 when excited to higher energy level upon photoirradiation. Our interest was to investigate the CPL induced photoresolu-
33 Resistance against photodestruction, high light absorption at tion in which the racemization of enantiomers may occur even
34 UV-visible window (high g factor) and thermal stability of at the electronic ground state. For this purpose, we utilized
35 enantiomers are additionally required to achieve an efficient azobenzene based photochromic systems that has a unique
36 photoresolution by the CPL irradiation. Much of the earlier property of reversible photoisomerization. Upon suitable wave-
37 reports of photoresolution by the CPL demonstrated intercon- length light irradiation to azobenzene, E to Z isomerization
38 version of enantiomers at electronic excited state. For instance, results in isomers having different geometry, spectral features
39 sterically overcrowded chiral alkenes developed by Feringa and polarity.[23] Because azobenzene can be easily incorporated
40 et al. showed rapid photoisomerization of P-1 into M-1 at into molecular designs, several compounds having azobenzene
41 excited state without notable photodegradation.[11] Upon as a functional moiety has been synthesized that found
42 irradiation of the racemic 1 using CPL at 313 nm, stereospecific applications both in material and biological sciences.[23] Optical
43 photoisomerization occurred that reverse the helicity of the switches and memory devices based on azobenzene has been
44
45 Dr. P. K. Hashim received an MS in Organic Prof. Nobuyuki Tamaoki obtained his Ph.D
46 Chemistry from Aligarh Muslim University in degree from Chiba University in Japan. After
47 2008 and a Ph.D. in Biological Science in 2012 working as a researcher, a senior researcher
48 under the supervision of Professor Nobuyuki and a group leader at Japanese government’s
49 Tamaoki at Hokkaido University. His Ph.D. research institutes including National Institute
thesis focused on molecular chirality induction of Advanced Industrial Science and Technol-
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by polarized light in azobenzene derivatives. ogy he moved to Hokkaido University as a full
51 Currently he is a project researcher in the professor in 2008. Currently he is also a
52 group of Professor Takuzo Aida at The Uni- director of the Green Nanotechnology Center
53 versity of Tokyo. His research interests include of the University. His research interests include
54 (1) Molecular chirality introduction, photochemistry, stereochemistry, organic syn-
(2) supramolecular adhesives for nucleic acids thesis, molecular switches and motors and
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and proteins and (3) biomolecular-based func- self-assembled molecular systems.
56 tional nano-architectures.
57

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21 Figure 1. CPL-induced interconversion of compound 1–3 by a photoresolution process. (a) Overcrowded alkene developed by Feringa et al.[11] (b) Rigid bicyclic
22 system introduced by Schuster et al.[21] (c) Photochromic cyclooctene reported by Inoue et al.[22]
23
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25 demonstrated in the laboratory. Azobenzene derivatives also
26 have been investigated as a component of liquid crystals,
27 photonic crystals as well as organic conductors or gels.[24]
28 Using CPL as a chiral source, azobenzene-based polymers
29 and liquid crystals have also been studied to introduce chiral
30 molecular order in the assembly process.[25] Azobenzene
31 incorporated in a constraint cyclic structure having a chiral
32 element is particularly interesting because such structure can
33 be reversibly changed by E-Z photoisomerization of azoben-
34 zene. In 2006, we designed bicyclic azobenzene dimer 4 and
35 demonstrated the concept of ground state racemization of
36 enantiomers by photoisomerization (Figure 2).[26] When the
37 azobenzenes are in E form, the rigid conformation of cyclic ring
38 restricts the racemization process, while the Z-azobenzene with
39 bent geometry accelerate the racemization process. The planar
40 chirality can be generated in the compound 4, only when the
41 “flip-flop” process originated from the 2,2-diphenylpropane is
42 considerably slow. Additional chiral elements derived from the
43 E and Z-azobenzene, before or after photon irradiations is also
44 possible. Hence in the compound 4, a total of three pairs of Figure 2. Schematic showing the racemization and E-Z isomerization of
45 enantiomers coexists. Spectroscopic studies evidenced relative bicyclic azobenzene dimer 4 (a). Blue bars represent azobenzene units.
Interconversion of R or S enantiomers of 4 by r- or l-CPL irradiation.
46 populations of E,E, E,Z, and Z,Z isomers at PSS and the existence
Reproduced with permission from Ref. [26]. Copyright 2006, American
47 of planar chirality with corresponding enantiomers were Chemical Society.
48 confirmed by CD studies. The photochemical conversion from
49 (R)-E,E-4 to (S)-E,E-4 most likely involved at least four reaction
50 steps (Figure 2). Despite the complicated photochemical iso- 2.2. Photoresolution of Monocyclic Planar Chiral Derivatives
51 merization of compound 4, l- or r-CPL irradiations could
52 generate an enantiomeric imbalance, which was detectable in The partial photoresolution of bicyclic azobenzene dimer 4
53 CD spectrum. In this case, the enantiomeric excess of the E, E typically proceed through a four-step enantio-differentiating
54 isomer obtained by the CPL induced partial photoresolution photoisomerization path involving three isomers (EE, EZ and
55 was 1.1 %. Further, the entire process from racemic to partial ZZ). There is always a risk that the contribution from all
56 enantiomeric enrichment was repeatable for several cycles enantiomers might affect the assessment of actual enantio-
57 using polarized and nonpolarized light, respectively. meric enrichment produced by the CPL irradiation. We

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Figure 3. Structures of monocyclic planar chiral azobenene derivatives 5–10. Depending on the rotation preference of the naphthalene (5–7) or substitiuted
15 benzene (8–9) rotor, these molecules undergo racemization in E or Z state of azobenzene.
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18 developed a new set of monocyclic planar chiral azobenzene
19 derivatives to investigate reversible enantio-differentiating
20 photoisomerization by CPL irradiation (Figure 3).[27,28] Some of
21 these designs also utilized for the material applications as chiral
22 dopants in liquid crystals that show large helical twisting power
23 and reflection colors. These monocyclic azobenzene derivatives
24 consists of two segments, a rotor part based on substituted
Scheme 1. Diagram showing the enantio-differentiating photoisomerization
25 naphthalene or benzene and a photo switchable azobenzene pathways of chiral compounds under the influence of CPL irradiation.
26 part. The degree of restriction for the free rotation of rotor a) Compounds (e. g. compound 1) that undergo racemization between
27 segment is decided by the bulkiness of substituents as well as E enantiomers (R and S) at electronic excited state. b) Compound 10 with
racemization of enantiomers even at the electronic ground state of the
28 or Z form of azobenzene units present in the cyclic structure. Z form. Solid (high) and dotted (low) arrows represent the relative reaction
29 Importantly, these monocyclic derivatives show planar chirality rates of photoisomerization paths. Adapted with permission from Ref. [29].
30 only when the rotation of the rotor segment is sufficiently low. Copyright 2011, John Wiley and Sons.

31 For instance, compound 5 and 8 with bulky substituent or

32 short spacers, the free rotations of the rotor were completely
33 prevented even in the Z isomer of azobenzene. Hence a planar allow a fast rotation of the rotor segment. Compound 6 and 10
34 chirality with separable enantiomers of compound 5 and 8 were special in the sense that the rotation of the rotor is only
35 were possible.[27c,29] In contrast, the cyclic azobenzene 7 and 9 happen when azobenzene exists in the Z form. Accordingly,
36 with less bulky substituent such as fluorine on the rotor or compound 6 and 10 demonstrated chirality with separable
37 naphthalene rotor connected to the spacers at its para enantiomers in the E form of azobenzene. In other words, a
38 positions, no evidence of chirality was observed at room chirality ON-OFF switching, based on E-Z photoisomerization of
39 temperature, regardless of E or Z form of azobenzene units. azobenzene, is showed in the compound 6 and 10. The chirality
40 This is obvious considering the large space inside the ring that switching, either in electronic ground state or photoexcited
41 state is important to achieve partial photoresolution by CPL
42 irradiations. Many photochromic chiral molecules racemize at
43 the electronic excited state (Scheme 1a),[18,20] however the
44 monocyclic azobenzene 6 and 10 racemize in the electronic
45 ground state. Compound 10 had superior chiral stability in the
46 E isomer and fast racemization in the Z isomer (Figure 4).[29]
47 Upon CPL irradiation to E-10 at 488 nm, an active CD signal
48 was observed confirming the enrichment of one of the
49 enantiomers with respect to the other enantiomer (ee = 0.3 %).
50 Here the photoresolution most likely happened via chiral
51 discrimination at electronic ground state due to the racemiza-
52 tion possibility of compound 10 in the Z isomer. When a CPL is
53 irradiated to a racemic mixture of compound 10, preferential
54 interaction of one of the enantiomers with l- or r-CPL can
55 Figure 4. The formation of R or S enantiomers of monocyclic azobenzene 10 produce unequal E-Z isomerization, i. e. the isomerization paths
56 induced by r- or l-CPL irradiation. Adapted with permission from Ref. [29]. from R-to-R or S-to-S (solid and dotted line in Scheme 1) can be
57 Copyright 2011, John Wiley and Sons. different. This difference is translated further to preferred

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 Minireviews
1 enantiomer when the molecule undergoes repeated Z-E reverse
2 isomerization at PSS (thick line). We believe novel photo-
3 resolution mechanism, as in the case of simple cyclic
4 azobenzene derivatives, could be useful as a model system to
5 study further the asymmetric imbalances of biomolecules.
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8 3. CPL-Induced Absolute Asymmetric Synthesis
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10 Model organic compounds that demonstrate absolute asym-
11 metric synthesis by CPL irradiation is particularly attractive,
12 however only few systems satisfied the required set of
13 parameters such as strong optical rotatory power, preferential
14 light absorption at the start of a chemical reaction as well as
15 the successful transfer of chiral information into final products.
16 The groups of Kagan and Calvin independently reported the
17 first CPL directed asymmetric synthesis in a helicene
Figure 6. Molecular diagram showing the E-Z photochemical conversion of
18 compound.[12] Advantageously, helicenes are typically synthe- azobenzene dimers 12–14.
19 sized through a ring closure reaction mediated by light
20 irradiation (Figure 5). Thus, during the synthesis of helicene by
21 however EZ forms with ‘trans’ and ‘cis’ azobenzenes in the
22 same molecule showed chirality, where the enantiomers of 12–
23 14 can be separated by chiral chromatography. In the absence
24 of CPL, the EZ forms always racemic as evident from the equal
25 intensity but with opposite signs of CD spectra. The EZ forms
26 can be photochemically converted into EE and ZZ indicating
27 the existence of step-wise interconversion pathway of isomer-
28 ization, i. e. EE-EZ and EZ-ZZ. r- or l-CPL irradiation to
29 Figure 5. Absolute asymmetric synthesis of hexahelicene 11 using CPL. compounds 12 and 13 were not able to induce a detectable
30 chirality due to negligible g factor of the respective (R)-EZ and
31 (S)-EZ stereoisomers, which is difficult to observe experimen-
32 CPL, it was possible to achieve preferential excitation of tally by CD spectroscopy. Of note, the EZ isomeric composition
33 ground-state molecules with chiral information from irradiated of 12 and 13 at PSS436 is only 12 % (88 % constitute EE and ZZ
34 light and the same chirality can reflect the optical rotation of achiral isomers). However, compound 14 showed relatively
35 obtained helicene. However, the observed optical rotation is large g value and EZ ratio (24 %) compared to 12 and 13 at
36 low, most likely due to the aryl-ethylene bond rotation at the PSS436 and hence an induced CD by CPL irradiation was
37 excited singlet state that causes the equilibration of the two detected. r- and l-CPL successive irradiations to EE-14 produced
38 unequally excited enantiomers. In search of developing a new opposite cotton effects confirming the tunability of enantio-
39 molecular system capable of generating selective enantiomer meric excess in R or S enantiomers of EZ-14. A photoracemized
40 directly from a prochiral molecule by CPL irradiation, as well as state with no chirality preference is obtained when a non-
41 its reversible control by changing handedness of CPL, we polarized light is irradiated to EE-14, instead of CPL (Figure 7).[32]
42 designed a new set of azobenzene derivatives (Figure 6).[30–32] In Under r- or l-CPL irradiation, the R and S enantiomers of the EZ
43 the design, a prochiral azobenzene dimer, by photoirradiation, form of azobenzenes can be preferentially photoisomerized
44 first generates chirality (point, axial or planar) in the structure into nonchiral EE or ZZ at ground states (or the reverse non-
45 and then undergo an enantio-differentiating photoisomeriza- enantiodiscriminating photoisomerization between EE or ZZ to
46 tion at the ground state. In the case of compound 12, EZ). In this case, EZ to EE or ZZ photoisomerization that
47 azobenzenes were directly introduced into a sp3-hybridized repeatedly occur could be responsible for causing an enantio-
48 carbon having a methyl and phenyl group so that by photo- meric imbalance in the system at the PSS. The CPL-induced
49 irradiation point chirality can be generated at the carbon atom. reactions of EE-14 to form a preferred chiral product can be a
50 Whereas in compound 13, azobenzenes were part of the [2.2] new mechanism for the absolute asymmetric synthesis,
51 paracyclophane, which facilitates generation of planar chirality because the process involve a direct conversion of achiral
52 by photoirradiation. For the axial chirality induction by photo- compound into one enriched enantiomer without any source
53 irradiation, as in compound 14, phenylazo moieties were of chemical chirality. Alternatively, this can be a simultaneous
54 connected to a common benzene ring having a naphthyl unit generation of asymmetry and photoresolution in the prochiral
55 at its ortho position. Light irradiation of suitable wavelength to molecule by a single wavelength CPL irradiation.
56 compounds 12–14 can produce a total of three isomers (EE, EZ,
57 and ZZ). EE and ZZ isomers do not have any chiral element,

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1 In the case of photochirogenesis by CPL irradiation, the
2 experimentally observed enantiomeric excess, either via photo-
3 resolution or absolute asymmetric synthesis, is extremely small
4 and an amplification method is necessary. For instance, CPL
5 induced photoresolution of overcrowded alkene system re-
6 ported by Feringa et al., the enantiomeric excess was only
7 0.07 %, however this small excess of one of the enantiomers
8 can be amplified by using liquid crystal (LC) host materials,
9 which is highly sensitive to chiral perturbations. Nematic to
10 cholesteric phase transition in LC host can be easily achieved
11 by the addition of small amount of chiral guest molecule.
12 Racemic 1 (20 weight %) produced a nematic LC phase, which
13 converted into cholesteric phase upon irradiation at 313 nm
14 with r- or l-CPL due to the generation of one of the
15
Figure 7. Molecular diagram showing the asymmetric synthesis of com-
enantiomers in slight excess. The authors able to reversibly
16 pound 14 directly from the prochiral azobenzene EE-14 induced by r- or l- switch the chiral arrangements of a large number of LC
17 CPL irradiation. molecules by selective photoresolution of guest molecule
18 induced from r- or l-CPL irradiations.[11]
19 Asymmetric autocatalysis stands one of the well-established
4. Chiral Amplification
20 mechanisms that can dramatically amplify small enrichment of
21 one of the enantiomers by r- or l-CPL irradiations.[39] Soai et al.
22 Photochemical conversion of a racemate into a chiral com- reported for the first time an experimental evidence of
23 pound having only one enantiomer is obviously challenging asymmetric autoamplification in the chemical reaction of
24 due to entropically disfavoured deracemization process. Com- dialkylzinc and pyrimidine aldehydes with an enhanced ee
25 pared to CPL triggered chirality induction, where the ee is value of 88 % in the chiral product, in which the initially formed
26 extremely low, asymmetric photosensitization method that chiral product served as chiral catalyst to consecutive amplifica-
27 requires a small amount of a chiral source showed promising tion reactions.[40,41] Further investigations from the same group
28 results towards the photochirogenesis with enhanced enantio- demonstrated that an external chiral factor with no detectable
29 meric excess.[33] Inoue et al. reported enantio-differentiating chirality (cryptochirality) could also be amplified using asym-
30 photoisomerizations of cycloalkene derivatives sensitized by metric autocatalysis process.[42] Importantly, the external chiral
31 point-chiral benzene (poly)carboxylates or planar chiral para- factor can control the sense of enantiomer produced after
32 cyclophane carboxylates with ee of up to 87 %.[34] A recent amplification. Thus, upon l-CPL (313 nm) irradiation to the
33 study using photochemically active chiral allene derivatives 15 racemic alkanol 16, asymmetric photodegradation of (R)-
34 deracemize with high enantioselectivity (ee upto 97 %) upon pyrimidyl alkanol 16 produced a cryptochiral (S)-16 with slight
35 visible light irradiation (λ = 420 nm), but a catalytic amount of a enantiomeric excess. Upon addition of fresh reactant (dialkyl-
36 chiral sensitizer is required (Figure 8).[35] The key observation in zinc and pyrimidine aldehydes) to the l-CPL irradiated mixture
37 this study is the significant difference in the triplet energy of alkanol 16, highly enantioenriched (S)-alkanol 16 with
38 transfer from photoexcited sensitizer to one of the two > 99.5 % ee was produced as a result of asymmetric autocatal-
39 enantiomeric forms of allenes that affects the overall sensitiza- ysis (Figure 9). Similarly, r-CPL (313 nm) irradiation followed by
40 tion rates of enantiomers. The formation of single enantiopure asymmetric autocatalysis produced (R)-16 with > 99.5 % ee.
41 compounds directly from a racemic mixture using chiral
42 sensitizer appeared to be an exclusive approach towards the
43 creation of asymmetry. Photochromic reactions of diarylethenes
44 with enantioselectivity by the influence of a chiral crystalline
45 state,[36] hydrophobic pockets of serum albumin protein[37] and
46 double helices of nucleic acids also have reported.[38]
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54 Figure 9. Diagram showing the formation of near enantiopure R- or S-16
55 induced by r- or l-CPL irradiation followed by asymmetric autocatalysis.
56 Figure 8. Diagram showing the photochirogenesis of the racemic mixture of
57 15 into a major enantiomer, ent-15, in the presence of a chiral sensitizer.

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 Minireviews
1 Another interesting approach for the amplification of small
2 chiral bias is associated with supramolecular chirality.[43,44]
3 Previous investigations using covalent helical polymers showed
4 that the CPL chirality can be transferred to polymer helix.[45]
5 Recently Kim et al. reported enantioselective helical stacking of
6 a triphenylamine (TPA) moiety after r- or l-CPL irradiation
7 during a self-assembly process (Figure 10).[46] In this system,
8
9
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11 Figure 11. Molecular structure of compound 18 and scheme showing the
12 cascade of events during the CPL-directed deracemization of racemic 18.
Reproduced with permission from Ref. [47]. Copyright 2009, Springer Nature.
13
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16 subjects because of the plausible explanation of homochirality
17 of biomolecules. CPL induced chirality in photochromic systems
18 has potential application as reusable memory devices as well as
19 optoelectronics,[7,11] although we have not discussed the details
20 Figure 10. Molecular structures of compound 17 and scheme showing the in this review. Previous decades demonstrated several exam-
induction and control of supramolecular chirality by r- or l-CPL irradiation.
21 ples of absolute asymmetric synthesis in model organic
Reproduced with permission from Ref. [46]. Copyright 2015, Springer Nature.
22 compounds as well as methods that employed for the chirality
23 transfer from a molecular level to supra- and macro- molecular
24 CPL induced small chiral bias of the TPA moiety is amplified levels.[48] Photochromic moieties such as azobenzene, over-
25 when TPA undergo an assembly process producing aggregates crowded alkene, cyclic alkene, etc., have been incorporated
26 with specific handedness. Authors designed this system such a into several molecular designs to meet prerequisite as a model
27 way that the handedness of helical structures either can be system to study enantioselective photochemical reactions.
28 reversibly switched by the alternate irradiations of r- or l-CPL, However, studies focusing the asymmetry introduction to
29 or can permanently locked. The locking process is achieved by fundamental biomolecules such as amino acids, nucleic acids,
30 the topochemical photopolymerization of the diacetylene (DA) peptides and proteins are scarcely reported,[49] partly due to the
31 moiety attached at the side chain of TPA moiety. Thus, the poor light absorption and circular dichroism by amino acids,
32 desired handedness obtained after r- or l-CPL irradiations can which typically used as a measure of induced chirality in
33 be permanently fixed by a second irradiation using circularly molecular systems. Additionally, molecular system capable of
34 polarized ultraviolet light (CPUL), which makes several covalent absorbing light in the near-infrared CPL is more suitable as
35 bonds with in the assembled structure. model system to investigate plausible explanation of biomo-
36 Vlieg et al. studied symmetry breaking using amino acid lecular homochirality. Advantageously, near-infrared light re-
37 derivatives via a single-step asymmetric amplification method, sponsive azobenzene photoswitches has developed recently,[50]
38 which typically involve a CPL irradiation and a grinding and by incorporating those moieties in a chiral system, it may
39 process.[47] They irradiated by r- or l-CPL to an acetonitrile possible to induce chirality even by using near-infrared CPL.
40 suspension of imine compound 18, followed by treatment with Although chirality induction in synthetic polymers by external
41 organic base to induce racemization in solution and then stimuli is reported,[51] studies focusing the chiral bias in the
42 grinded for several days. Initial point of the crystallization polymeric form of amino acids and peptides are poorly
43 mostly produces equal amounts of left- and right-handed examined. Even after a decade since the first experimental
44 crystals, however growing crystal that are in continuous contact observation of photoresolution process in overcrowded alkene
45 with the r- or l-CPL irradiated solution slowly transformed with systems, its potential to use as chiroptical switch in material
46 a strong chiral bias. The handedness of the CPL light decides application is still not well established. Asymmetric synthesis
47 the optical sense of final crystals (Figure 11). This example directly from non-chiral molecules triggered by chiral physical
48 clearly demonstrates the plausible usefulness of CPL in the forces is limited to few reports, however by the advancement
49 generation of asymmetry in molecules including amino acid of chemical catalysis achiral molecules can be converted into
50 derivatives, which is relevant for the origin of the homochirality chiral compounds with desired handedness, although the
51 present in the biological molecules. process is irreversible.[52] For the amplification process of CPL
52 induced chirality, various methods are developed such as
53 asymmetric autocatalysis, rotation induced molecular ordering
54 5. Summary and Outlook as well as supramolecular assembly. Yet, a complete symmetry
55 breaking with preferred handedness of chirality and high
56 Asymmetry introduction to molecular systems followed by enantiomeric excess is still unprecedented demanding the
57 chiral amplification by CPL irradiation is one of the important

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