Template-Directed Photochemical [2 + 2] Cycloaddition in Crystalline

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Template-Directed Photochemical [2 + 2] Cycloaddition in Crystalline Materials: A Useful Tool to Access Cyclobutane Derivatives Ming-Ming Gan, Jiangang Yu, Yao-Yu Wang, and Ying-Feng Han Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01308 • Publication Date (Web): 28 Dec 2017 Downloaded from http://pubs.acs.org on December 30, 2017

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Crystal Growth & Design

Template-Directed

Photochemical

[2

+

2]

Cycloaddition in Crystalline Materials: A Useful Tool to Access Cyclobutane Derivatives Ming-Ming Gan,† Jian-Gang Yu,*,†,‡ Yao-Yu Wang† and Ying-Feng Han*,† †

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, College of Chemistry and

Materials Science, Northwest University, Xi’an 710069, P. R. China ‡

College of Chemical and Material Engineering, Quzhou University, Quzhou 324000, P. R. China

ABSTRACT: The photochemical [2 + 2] cycloaddition reaction in crystalline materials is one of most important routes for the synthesis of cyclobutane compounds, which are otherwise difficult to prepare by conventional organic synthesis. In this perspective, a series of olefins that undergo photochemical [2 + 2] cycloaddition reactions is summarized and categorized according to their various functionality. Using these olefins, a range of cyclobutane derivatives were prepared by this [2 + 2] cycloaddition protocol.

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1. INTRODUCTION: Photochemical reactions are widely used in daily life, such as in printing, computing and healthcare. However, photochemical reactions are usually considered to be synthetic tools of last resort due to their low yields and selectivities.1-3 Nevertheless, a number of complex and exotic organic intermediates can efficiently be synthesized by photochemical reactions.4-9 Indeed, application of photochemical [2 + 2] cycloaddition reactions in the construction of cyclobutane derivatives has grown in popularity and become a highly active field of research.10-16 Because cyclobutane motifs were found in many complex natural compounds and its potential biological activity.17 During the past few decades, special attention has been paid to the structural transformations through photochemical [2+2] cycloaddition reactions in the solid states or crystals. In this area, organizing the two precursor olefin molecules into a suitable space is obligatory for satisfactory conversion of the photochemical reaction.18 During the 1960s, Schmidt et al.19-20 proposed a well-known topology for photochemical reactions based on the intensive study of the solid-state photochemistry of cinnamic acid derivatives. Furthermore, a minimum amount of atomic or molecular movement was also essential for inducing this solid-state reaction. According to Schmidtʹs postulates, the key to photochemical reaction under crystalline conditions is as follows: (1) the two olefins should be oriented in parallel; (2) the distance between these two olefins should be generally between 3.5 Å and 4.2 Å. In order to promote this reaction, several protocols were developed. For instance, MacGillivray et al.21 applied hydrogen-bond-driven or coordination-driven self-assembly. Harada and Ogawa et al.22 presented a study of the effects of the pedal motion in solid-state reactions. Vittal et al.1,23 studied single-crystal to single-crystal (SCSC) [2 + 2] photodimerizations of 3D metal-organic frameworks. Ramamurthy and Sivaguru et al.2 presented diverse organic structures, such as solvent-free crystals and water-soluble host-guest assemblies, which were found to be efficient synthetic tools to control [2 + 2] photodimerization. This perspective is focused on the current state of the art of photochemical [2 + 2] cycloaddition reactions of different kinds of functionalized olefins, for construction of a variety of cyclobutane derivatives. Herein, we have summarized and categorized the research progress of this chemistry according to the various functionalities of the olefins. From these olefins, a number of different types of cyclobutane derivatives were achieved by this protocol.


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2. PYRIDYL GROUPS 2.1. BISPYRIDYL GROUPS 1,2-Bis(4-pyridyl)ethylene (4,4ʹ-bpe, 1, Scheme 1) is one of the most frequently studied olefins in terms of the [2 + 2] photodimerization reaction. This unit has been shown to undergo photochemical cycloaddition using a range of templates, such as diols24, thioureas25,26, and dinuclear iridium or rhodium complexes,27-30 to produce rctt-tetrakis(4-pyridyl)cyclobutane (4,4ʹ-tpcb, 2, Scheme 1). This work has already been summarized in a number of reviews.1-3,6-9,20-22,31 Readers are advised to consult these articles for details.32-40 For example, a dinuclear molecular clip template in the form of organometallic macrocycle facilitate a [2+2] photochemical

[2

+

2]

reaction

between

two

coordinated

bpe

ligands

in

a

single-crystal-to-single-crystal transformation (Figure 1).30

Scheme 1

Figure 1. Formation of 2 from 1 under an organometallic macrocycle template in SCSC transformation. (Color: iridium, cyan; oxygen, red; nitrogen, blue; carbon, gray). Modified and reproduced from ref 30. Copyright 2008 Royal Society of Chemistry. In addition to 4,4ʹ-bpe, other kind of bispyridylethylenes (with the different pyridyl substitution positions) were also utilized in [2 + 2] photodimerization chemistry, as shown in Table

1.

MacGillivray

et

al.41,42

presented

the

assembly

of

trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (2,4ʹ-bpe, 3) with a linear template (4-chlororesorcinol) to

afford

2(4-chlororesorcinol)‧2(2,4ʹ-bpe).

After

irradiation,

a

single

product,



Page 4 of 32

rctt-1,2-bis(2-pyridyl)-3,4-bis(4-pyridyl)cyclobutane (2,4ʹ-tpcb, 4), was obtained in almost quantitative yield. Subsequently, trans-1-(2-pyridyl)-2-(3-pyridyl)ethylene (2,3ʹ-bpe, 5) was co-crystallized with resorcinol to give a 2(resorcinol)‧2(2,3ʹ-bpe) assembly.43 This was then irradiated,

providing

rctt-1,2-bis(2-pyridyl)-3,4-bis(3-pyridyl)cyclobutane

(2,3ʹ-tpcb,

6).

Trans-1-(2-pyridyl)-2-(2-pyridyl)ethylene (2,2ʹ-bpe, 7) was unexpectedly co-crystallized with catechol via hydrogen bonding to form a supramolecular six-component assembly. This supramolecular unit was shown to undergo [2 + 2] photodimerization in the solid state to give rctt-tetrakis(2-pyridyl)cyclobutane (2,2ʹ-tpcb, 8) stereoselectively and in quantitative yield.44,45 Liu et al.46-48 demonstrated the coordination of metal ions with an unsymmetrical olefin, trans-1-(3-pyridyl)-2-(4-pyridyl)ethylene, (3,4ʹ-bpe, 9). Upon UV irradiation, a [2 + 2] photocycloaddition reaction took place and afforded head-to-head (HH) and head-to-tail (HT) photodimer isomers of cyclobutane derivatives, 10 and 11 with absolute regiospecificities. Table 1 Precursor (olefins)

Product (cyclobutanes)

Refs

41-42

43

44-45

46-48

2.2. ARYLPYRIDYL GROUPS


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Arylvinylpyridine was also shown to be able to undergo [2 + 2] photodimerization in a well-assembled form. As shown in Scheme 2, several phenylpyridylethylenes (12a-p) were disclosed to proceed photochemical [2 + 2] cycloaddition reactions in crystalline states. Eventually, HT products (13a-p) can be regioselectively obtained by applying different templates.25,26,49-60 The packing arrangement of olefins in solid/crystal are generally the essential of the regiospecific photodimerization reactions. Yamada et al.49 described the essential role of pyridinium-π interactions between 4-styrylpyridine (4-spy, 12a) in acidic media, which gave a HT product (13a) after photochemical [2 + 2] cycloaddition. Pyridinium-π interactions between substrates also resulted in the selective formation of the HT dimer (13a) during the photolysis.50 In some cases, HH products, 13aʹ, 13bʹ, 13gʹ, 13iʹ, 13lʹ and 13mʹ can also be formed (Scheme 2). For example, 4-spy (12a) coordinated to Ag(I) ions and formed an assembly via Ag···Ag and Ag···C(phenyl) interactions. The metal-organic solid [Ag2(12a)4][CF3SO3]2 underwent [2 + 2] photodimerization to give a cyclobutane product 13aʹ stereoselectively and quantitatively (Figure 2).58 Compound 12m co-crystallized with Ag(I) to form a metal-organic complex, which forms face-to-face perfluorophenyl-perfluorophenyl interactions (C6F5···C6F5) and argentophilic forces (Ag···Ag),

was

found

to

undergo

[2

+

2]

photodimerization

to

synthesize

rctt-1,2-bis(pentafluorophenyl)-3,4-bis(4-pyridyl)cyclobutane (13mʹ) (Figure 3).59

12

R

Precursor (olefins)

a

H

12a

b

4-CN

12b

Product (cyclobutanes) 13a

Refs 25, 49-54

13aʹ

52, 54, 55, 58

13b

55, 56

13bʹ

25, 55, 56

c

4-F

12c

13c

25, 53, 54, 55, 57

d

4-Cl

12d

13d

25, 53, 54, 55, 57

e

4-Br

12e

13e

25, 53, 54, 55, 57



f

4-I

12f

g

4-Me

12g

Page 6 of 32

13f

25, 53, 54, 55, 57

13g

25, 53, 55, 56

13gʹ

55

13h

53

13i

49, 53, 54

13iʹ

49

h

4-Et

12h

i

4-CF3

12i

j

4-OMe

12j

13j

25, 49, 53, 54

k

2-OMe

12k

13k

53

3,5-Cl2

12l

13l

25, 54

l

13lʹ

25, 53

2,3,4,5,6-F5

12m

13m

53, 54

m

13mʹ

59

n

4-NO2

12n

13n

53

o

4-CH2NH2

12o

13o

60

p

4-OH

12p

13p

57

Scheme 2

Figure 2. Formation of 13aʹ from 12a under silver ion template in SCSC transformation. (Color: silver, pink; oxygen, red; nitrogen, blue; carbon, gray; sulfur, yellow; fluorine, green.). Modified and reproduced from ref 58. Copyright 2014 American Chemical Society.


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Figure 3. Formation of 13mʹ from 12m under silver ion template. (Color: silver, pink; oxygen, red; nitrogen, blue; carbon, gray; sulfur, yellow; fluorine, green). Modified and reproduced from ref 59. Copyright 2014 American Chemical Society. 4-Cl-stilbazole (12d) and 4-Me-stilbazole (12g) could been templated by resorcinol through a ditopic

hydrogen-bond-donor

interaction

(Figure

4).

The

compound

underwent

a

cross-photodimerization reaction in the solid state to provide cyclobutane compound 14 (Scheme 3).61

Scheme 3

Figure 4. Formation of 14 from 12d and 12g under resorcinol template. (Color: oxygen, red; nitrogen, blue; carbon, gray; fluorine, green). Modified and reproduced from ref 61. Copyright 2012 Royal Society of Chemistry. Cycloaddition between phenyl and olefinic C=C bonds is rare. Vittal et al.62 showed that the compound 2-fluoro-4ʹ-styrylpyridine (15) in Zn2(ptol)4(15)2 (ptol = para-toluate) underwent an unusual photochemical [2 + 2] cycloaddition reaction between the fluorophenyl group and an



Page 8 of 32

olefinic C=C bond to generate bicyclo[4.2.0]octa-2,4-diene derivative 16 (Scheme 4). Furthermore, compound 16 was relatively thermally unstable and cleaved reversibly back to compound 15 when heated.

Scheme 4 In

addition,

(naphthalen-2-yl)vinylpyridine

[4-(2-npy),

17a],

and

4-(2-(naphthalen-1-yl)vinyl)pyridine (4-npy, 17b) could be assembled by Zn(II) centers linked by the dianion of 4,4ʹ-oxydibenzoic acid, facilitating photochemical [2 + 2] cycloaddition and resulting in the formation of 1,3-bis(4-pyridyl)-2,4-bis(naphthalen-2-yl)cyclobutane (18a) and rctt-1,3-bis(4-pyridyl)-2,4-bis(1-naphthyl)cyclobutane (18b), respectively (Scheme 5).51 The compound trans-1-(4-pyridyl)-2-(3-thienyl)ethylene (β-PTE, 17c) was assembled by using 4,6-diiodo-res (4,6-diI-res) into a co-crystal of composition (4,6-diI-res)·2(17c).63 This assembly underwent

intermolecular

[2

+

2]

photocycloaddition

to

provide

HH

product

rctt-1,2-bis(4-pyridyl)-3,4-bis(3-thienyl) (18c) stereoselectively in near-quantitative yield (Scheme 5).

Scheme 5 Two unsymmetrical olefins containing benzimidazole and 4-/3-pyridyl moieties (19a,b) were coordinated to Cd(II) or Zn(II) to form coordination polymers.64 The olefins of 19a and 19b were


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found to be in the alignment required for [2 + 2] photodimerization. Indeed, full conversions of 19a,b to 20a,b were obtained in the solid state upon irradiation, respectively (Scheme 6).

Scheme 6 1,8-Bis[(E)-2-(4-pyridyl)ethenyl (21) was photostable as indicated by exposure to UV light for a period time of ca. 40 h without any transformation (Scheme 7). However, the dinuclear complexes 2(21)·2AgX (X- = CF3SO3–, CH3C6H4SO3–, and ClO3–) underwent intramolecular [2 + 2] photodimerization in the solid state, affording cis-di(4-pyridyl)naphthocyclobutane (22) in moderate to high yield (Figure 5).65

Scheme 7

Figure 5. Formation of 22 from 21 under silver ion template. (Color: silver, pink; oxygen, red; nitrogen, blue; carbon, gray; sulfur, yellow; fluorine, green). Modified and reproduced from ref 65. Copyright 2015 American Chemical Society.



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2.4. PYRIDINE- AND CARBOXYLIC-ACID-SUBSTITETED GROUPS Pyridine- and carboxylic-acid-substituted olefins were also tested for their ability to undergo photochemical [2 + 2] cycloaddition reactions. The compound trans-3-(4-pyridyl) acrylic acid (4-PA, 23) reacted with CF3CO2H or H2SO4 to form salts with different patterns in the solid states, and photolytically provided 2,4-bis(4-pyridyl)-cyclobutane-1,3-dicarboxylic acid (24) and 3,4-bis(4-pyridyl)-cyclobutane-1,2-dicarboxylic acid (25), respectively (Scheme 8).66 In the solid state of 4-PA in the presence of CF3CO2H, 4-PAH+ cations were found in infinite parallel orientation in head-to-tail fashion, however, the orientation of 4-PAH+ cations was found to be in head-to-head fashion when H2SO4 was introduced. As a result, two stereoisomers of cyclobutane derivatives were stereoselectively synthesized by a solid-state photochemical [2 + 2] cycloaddition reaction quantitatively. The same group found that the anions of these salts play a key role in directing the packing of 4-PAH+ in the solid state. The selective formation of HT-photodimer 24 (Scheme 8) was also realized when he anions Cl–, ClO4–, and BF4– were used.67 Similarly, trans-3-(2ʹ-pyridyl)acrylic acid (2-PA) was combined with HCl, CF3CO2H, and H2SO4 to give 2,4-bis(2ʹ-pyridyl)-cyclobutane-1,3-dicarboxylic acid (HT-rctt-2,2ʹ-BPCD) in the context of [2 + 2] cycloaddition reaction in the solid states.68 In addition, the HH orientation of trans-(3ʹ-pyridyl) acrylic acid (3-PA) was shown to flip to HT with the ClO4− salt to produce HT-rctt-3,3ʹ-BPCD.

Interestingly,

both

the

HT-

and

HH-dimers

of

trans-2-(4-pyridyl)-4-vinylbenzoic acid (HPVBA) could be obtained from H2SO4 by changing its concentration during crystallization. Both salts undergo photodimerization in HH or HT fashion resulting in the formation of the corresponding products.69,70

Scheme 8


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Biradha et al.71 showed that the unsymmetrically substituted olefins 4-pyridylacrylamide (26a), and the methyl ester of 4-pyridylacrylic acid (26b), coordinated with Ag(I) to form the complexes [Ag(26a)2(NO3)], and [Ag(26b)2(NO3)]‧MeOH. Irradiation of these complexes afforded HH dimers 27a,b (Scheme 9) in nearly quantitative yield (Scheme 9).

Scheme 9

Unsymmetrical olefins containing amide groups (UBO) were tested for their ability to undergo photochemical cycloaddition reactions.72 The pure organic UBO materials 27a and 27b were shown to provide HH/HT dimers, 28a,b/28aʹ,bʹ, under different conditions (Scheme 10). For example, the formation of 28a from 27a was realized by SCSC transformation in the presence of silver ion template (Figure 6).

Figure 6. Formation of 28a from 27a under silver ion template in SCSC transformation. (Color: silver, pink; oxygen, red; nitrogen, blue; carbon, gray). Modified and reproduced from ref 72. Copyright 2016 American Chemical Society.



Page 12 of 32

Scheme 10 4-Azachalcone hydrochlorides were arranged using cation-π interactions, and selectively provided

HT

dimers

after irradiation.73 The compounds

4-azachalcone (29a) and

4ʹ-methoxy-4-azachalcone (29b) underwent [2 + 2] photodimerization as their HCl salts in the solid state to give HT dimers in quantitative yields. Later, exposure of crystalline 4-azachalcones to HCl gas produced the corresponding HCl salts, which underwent photochemical [2 + 2] cycloaddition reactions to give HT dimers (30a,b) in their crystals (Scheme 11).74

Scheme 11 In 2016, the trisubstituted pyridyl olefins 31a and 31b were introduced and coordinated with Ag(I)X to obtain the metal-organic solids [Ag(31a)2](OTs)·3(H2O) and [Ag2(31b)4][OTf]2.75 These assemblies were then photolytically reacted to generate 32a and 32b, respectively (Scheme 12).


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Scheme 12 The compound (E)-methyl-3-(pyridin-3-yl)prop-2-enoate (3-PAMe, 33) was assembled by 4,6-di-X-res (X = Cl, Br, I; res = resorcinol) and subsequently underwent two sorts of photo-induced cycloaddition in the solid state to provide cyclobutane compounds 34 and 34ʹ, respectively, according to the template (Scheme 13).76,77

Scheme 13 Trans-cinnamaldehyde 35 was coordinated to [Ag(cpi)CO2CF3]n (cpi = cinnamaldehyde N-(4-pyridyl)imine) and underwent a regioselective [2 + 2] photodimerization to form 1,3-bis((4-pyridyl)imine)-2,4-bis(phenyl)cyclobutane (cpi-cb, 36, Scheme 14).78 The pyridyl group was then removed to afford the aldehyde-functionalized cyclobutane α-truxilaldehyde.

Scheme 14 3. ARYL GROUPS Diphenylethylene (37) underwent sliding/pedal motion to meet Schmidt’s criteria in the solid state.22 Solid-state photo-induced cycloaddition of olefin bonds can afford cyclobutane compound (38, Scheme 15). In contrast, intramolecular cyclization between phenyl group and olefinic bond was observed in solution to generate compound 38ʹ (Scheme 15).62



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Scheme 15 Vishnumurthy et al.79 reported the [2 + 2] photodimerization of fluoro-substituted compounds 1-pentafluorophenyl-4-(4-methoxyphenyl)buta-1,3-diene, 1-pentafluorophenyl-4-(4-methylphenyl)-buta-1,3-diene

and

1-pentafluorophenyl-4-phenylbuta-1,3-diene in the solid state, giving three cyclobutane products. Resnati et al.80 introduced compound 39, containing iodotetrafluoro benzenes, which underwent head-to-tail photodimerization to give the product 40 in 80% yield (Scheme 16). In 2016, MacGillivray et al. reported that trans-1,2-bis(4-iodotetrafluorophenyl)ethane was able to assemble with 1,8-di(4-pyridyl)naphthalene (DPN) to form a 2(DPN)·2 assembly through N···I halogen

bonds,

which

subsequently

resulted

in

the

stereoselective

formation

of

rctt-1,2,3,4-tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)cyclobutane quantitatively.81

Scheme 16 Mei et al.

82

presented a “green” stereoselective [2 + 2] photodimerization of menadione (41.

Only one photoproduct 42 was formed when the photoreaction was carried out in the solid state or in the single crystal, however, two photoproducts 42 and 42ʹ were obtained in the solution


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(Scheme 17). The products could be isolated and further recycled by simple sublimation and condensation after photoreaction.

Scheme 17 4. CARBOXYLIC ACID GROUPS Trans-4,4ʹ-stilbenedicarboxylic acid (H2SDC, 43, Scheme 18) was found to react with 1,3-diaminopropane (DAP) and subsequently underwent photodimerization in the solid state to give rctt-1,2,3,4-tetrakis-(4ʹ-carboxyphenyl)-cyclobutane (TCCD, 44), quantitatively (Figure 7).83 A series of metal salts formed “supramolecular synthons” when combined with various amines, providing 1,2,3,4-tetrakis-(4ʹ-carboxyphenyl)cyclobutane via photochemical [2 + 2] cycloaddition.84 A metal-organic salt of K2SDC was also successfully utilized to form K4TCCB·4H2O

(H4TCCB

=

tetrakis-1,2,3,4-(4ʹ-carboxyphenyl)cyclobutane).85

The

photoproduct additionally underwent the reversible cleavage of its cyclobutane ring. Three alkali metal salts of trans,trans-muconate (muco) led to the formation of Li2muco, Na2muco, and K2muco, respectively.86 These salts underwent a [2 + 2] photodimerization and subsequent Cope rearrangements to yield cycloocta-3,7-diene-1,2,5,6-tetracarboxylate in the crystalline state.

Scheme 18



Page 16 of 32

Figure 7. Formation of 44 from 43 under DAP template. (Color: oxygen, red; nitrogen, blue; carbon, gray). Modified and reproduced from ref 83. Copyright 2010 Royal Society of Chemistry. Fumaric

acid

(45)

was

assembled

with

a

linear

template,

2,3-bis(4-methylenethiopyridyl)naphthalene (2,3-nap), into a 2(2,3-nap)·2(45) structure via hydrogen bond interactions (Figure 8).87 This assembly provided rctt-1,2,3,4-tetracarboxylic acid (rctt-cbta, 46, Scheme 19) in up to 70% yield via stereoselective [2 + 2] photodimerization. Similarly,

compound

45

was

also

assembled

with

a

highly

congested

1,8-diheteroarylnaphthalene template to form the rigid structure which provided a cis,trans,cis-cyclobutanetetracarboxylic acid via stereoselective photodimerization.88

Figure 8. Formation of 46 from 45 under 2,3-nap template in SCSC transformation. (Color: oxygen, red; nitrogen, blue; carbon, gray; sulfur, yellow). Modified and reproduced from ref 87. Copyright 2005 Royal Society of Chemistry.

Scheme 19


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As shown in Scheme 20, a series of carboxylic acid substituted olefins could undergo [2 + 2] photodimerization in the solid state to produce corresponding cyclobutane products with the assist of suitable templates.89-100 Trans-cinnamic acid (47a) could be assembled using a double salt of diamines, and underwent [2 + 2] photodimerization in the solid state to mainly give β-truxinic acid (48aʹ).92 Similarly, trans-2,4-dichlorocinnamic acid reacted with the diamine double salt of 1,2-trans-diaminocyclohexane to give a β-dimer via [2 + 2] photodimerization.89 For instance, Kariuki et al.95 reported two polymorphs of 3-fluoro-trans-cinnamic acid (β1 and β2, 47b). Both polymorphs underwent photochemical [2 + 2] cyclodimerization upon UV irradiation to produce 3,3ʹ-difluoro-β-truxinic acid (48b) in almost quantitativeyield. In 2013, Sparkes et al.97 pointed out that 4-bromo-trans-cinnamic acid (47d) possessed a temperature-dependent phase transition. A head-to-head [2 + 2] photodimerization reaction took place in the solid state to produce a carboxylic acid dimer (48dʹ, Scheme 20). Taddei et al.98 reported a new molecular salt [(4-aminocinnamic acid)H]Br with two polymorphic modifications.

48

R

Precursor

Product

(olefins)

(cyclobutanes)

Refs

48a

89, 90, 91

48aʹ

89, 92, 93, 94

47b

48bʹ

95

4-Cl

47c

48cʹ

89, 96

d

4-Br

47d

48dʹ

96, 97

e

4-NH2

47e

48e

98

f

4-NO2

47f

48fʹ

99

g

2,4-Cl2

47g

48gʹ

89

h

3,4-Me2

47h

48hʹ

100

a

H

b

3-F

c

47a

Scheme 20



Page 18 of 32

Recently, Wheeler et al.90,91,101-103 presented multi-molecular photodimerization reactions of sulfonamidecinnamic acids (49a,b, Scheme 21) to form “fish hook” topologies (Figure 9), giving head-to-tail supramolecular dimers in single-crystal to single-crystal transformation in quantitative yield (50a,b, Scheme 21).

Scheme 21

Figure 9. Formation of 50a from 49a in SCSC transformation. (Color: oxygen, red; nitrogen, blue; carbon, gray; sulfur, yellow). Modified and reproduced from ref 90. Copyright 2011 Royal Society of Chemistry. The co-crystals of trans-cinnamamide (51) and phthalic acid were shown to produce β-type photodimer (52) under a Hg lamp via a head-to-head [2 + 2] cycloaddition (Scheme 22).93 In 2010,

Wolf

et

al.100

demonstrated

the

assembly

of

cinnamoyl

units

using

1,8-bis(3ʹ-methyl-4ʹ-anilino)naphthalene and 1,8-bis(4ʹ-anilino)naphthalene. The compound 53 was irradiated under UV light to produce β-truxinic acid. Furthermore, the template was quantitatively recovered by an acid mediated hydrolysis to obtain compound 54 (Scheme 23).

Scheme 22


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Scheme 23 5. MULTI OLEFINIC GROUPS Pyridine functionalized conjugated diene 55 was applied in photoreaction to form [3]ladderane in solid state. These assembles were further irradiated to conduct [2 + 2] cycloaddition reaction to produce ladderanes (56, Scheme 24).104,105 Lang et al.106-108 continuously worked on [2 + 2] photodimerization of diene 55. Two respective products 56 and 57 were independently observed by using different templates through single-crystal-to-single-crystal transformation.

Scheme 24 The compound 4-pyr-poly-3-ene (58) was assembled by 5-methoxyresorcinol (5-OMe-res) to give 2(5-OMe-res)·2(58) (Figure 10). It was applied in photochemical reaction to form [5]ladderane (59) in the solid state (Scheme 25).104,105 In this process, the conjugated olefins were converted to ladderanes stereospecifically on a gram scale quantitatively.

Figure 10. Formation of 59 from 58 under linear template 5-OMe-res. (Color: oxygen, red; nitrogen, blue; carbon, gray). Modified and reproduced from ref 104. Copyright 2004 Wiley-VCH.



Page 20 of 32

Scheme 25

Ligand 60 was assembled using 4-benzylresorcinol to form a crystalline sample of a 2(60)·2(4-benzylresorcinol) structure. Upon irradiation, cycloaddition was realized to stereoselectively construct p-cyclophane 61 on a gram scale (Scheme 26).109-111 Remarkably, only one pairs of olefin double bond of ligand 60 reacted and initiated to undergo [2 + 2] photocyclolization when the photochemical reaction was performed in solution (Scheme 26).108

Scheme 26 Recently, Biradha et al.

112

systematically studied the use of bisamide derivatives in solid-state

[2 + 2] photodimerization. A four-twelve-four fused tricyclic compound containing a tetraamide macrocycle was stereospecifically synthesized by [2 + 2] cycloaddition in the solid state. The compound N,Nʹ-bis(3-(4-pyridyl)acryloyl)hydrazine (62) was assembled by using AgNO3 and AgClO4 to form [Ag(62)(NO3)], [Ag(62)(ClO4)] structures. These gave a different cyclobutane product 63 and a four–twelve–four fused tricyclohexadecane 63ʹ ring system after irradiation, respectively (Scheme 27).


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Scheme 27 Similarly, several derivatives of bisamides (64a-c, Scheme 28) containing 3-pyridyl and phenyl groups and aliphatic groups as linkers have been reported recently.5 Afterwards, cyclobutane compounds (65a-c, Scheme 28) were synthesized from these bisamide derivatives via [2 + 2] photodimerization reaction under the help of templates.113-115 N

N

O HN

hv

X HN

O

O

N H N

Ag(I) O

X

N H

H N

O

X

N H N

O

N

65a,b,c N 64a,b,c

a: X = (CH2)2

b: X = (CH2)4

c: X = H2C

CH2

Scheme 28 Biradha et al.116-118 found that 66 (Scheme 29) could be assembled by using phloroglucinol (PG) as template, and that the product underwent a very fast photochemical reaction to provide tricyclo[6.2.0.03,6]decane (67, Figure 11). However, the resorcinol was not able to promote double [2 + 2] photodimerization. Moreover, compound 67 could be successfully separated from PG using triethylamine hydrochloride.



Page 22 of 32

Scheme 29

Figure 11. Formation of 67 from 66 under silver ion template. (Color: silver, pink; oxygen, red; nitrogen, blue; carbon, gray). Modified and reproduced from ref 118. Copyright 2013 Wiley-VCH. Vishnumurthy et al.119 reported a head-to-tail [2 + 2] photodimerization of the fluoro-substituted compounds 1-pentafluorophenyl-4-(4-methoxyphenyl)buta-1,3-diene (68a), 1-pentafluorophenyl-4-(4-methylphenyl)-buta-1,3-diene

(68b)

and

1-pentafluorophenyl-4-phenylbuta-1,3-diene (68c) in solid state, giving three cyclobutane products 69a-c, respectively (Scheme 30).

Scheme 30 Trans,trans-muconate (muco, 70, Scheme 31) was reacted with Na/K hydroxides to form the corresponding alkali metal salts Na/K2muco.120 These salts underwent a [2 + 2]


Page 23 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


photodimerization

and

subsequent

Cope

rearrangements

to

yield

cycloocta-3,7-diene-1,2,5,6-tetracarboxylate 72 in the crystalline state in the crystalline (Scheme 31).

Scheme 31 6. N-HETEROCYCLIC CARBENE GROUPS Han et al.121,122 prepared two olefin-linked bis(NHC) ligands (NHC = N-heterocyclic carbene, 73a,b, Scheme 32), of the form NHC−Ar−C=C−Ar−NHC. These compounds reacted with two Ag(I) ions to form complexes 74a,b (Scheme 32) which underwent facile [2 + 2] photodimerization in the solution to give cyclobutane products 75a,b (Scheme 32), respectively. After removal of Ag(I), the cyclobutane-based polyimidazolium products (76a,b, Scheme 32) were obtained. However, the photochemical reactions of silver complexes 74a,b in the solid states failed. The intramolecular [2 + 2] cycloaddition reaction of 77a giving the cyclobutane derivative 78a in quantitative yield in the solid state. In contrast, the photochemical reaction of 77b in the solid state was quite slow and the conversion to 78b is only about 25% after 72 h (Scheme 33).

Scheme 32



Page 24 of 32

Scheme 33

Moreover, a synthetic strategy for the preparation of a series of polyimidazolium macrocycles containing terminal cinnamic esters was also developed. The length and width of the complex could be adjusted by altering the size and shape of the substituents on the ligands, and subsequently provided polyimidazolium macrocycles via [2 + 2] photodimerization.123-125 7. CONCLUSIONS In this perspective, a series of functionalized olefins are summarized in relation to their photochemical [2 + 2] cycloaddition chemistry. Based on the wealth of examples, the [2 + 2] photodimerization is already a very useful tool for the synthesis of cyclobutane derivatives. Moreover, the photoproducts have been applied in the synthesis of coordination polymers (CPs) such as MOFs. We believe that the future holds much promise for further research into the photochemical [2 + 2] cycloaddition reaction, leading to diverse photoproducts and applications.

AUTHOR INFORMATION Corresponding Author [email protected] (J.-G. Yu); [email protected] (Y.-F. Han) Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. Acknowledgements


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We gratefully acknowledge financial support from the NSFC (Nos. 21722105, 21371036 and 21531007), the Shaanxi Key Laboratory of Physical-inorganic Chemistry (17JS133) and FM＆ EM international joint lab of Northwest University. Yu is thankful to the China Postdoctoral Science Foundation (2017M613185) for a postdoctoral scholarship. REFERENCES

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Page 32 of 32

For Table of Contents Use Only

Template-Directed Photochemical [2 + 2] Cycloaddition in Crystalline Materials: A Useful Tool to Access Cyclobutane Derivatives Ming-Ming Gan, Jian-Gang Yu,* Yao-Yu Wang and Ying-Feng Han*

Graphic abstract The photochemical [2 + 2] cycloaddition reaction in crystalline materials has been hν

proved to be an efficient method for the formation of cyclobutane compounds.

single crystal

single crystal


Template-Directed Photochemical [2 + 2] Cycloaddition in Crystalline

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