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. 2024 Feb 26;9(16):17945–17955. doi: 10.1021/acsomega.3c09381

General Synthesis of meso-1,4-Dialdehydes and Their Application in Ir-Catalyzed Asymmetric Tishchenko Reactions

Runze Zhao 1, Ismiyarto 1, Da-Yang Zhou 1, Kaori Asano 1, Takayoshi Suzuki 1, Hiroaki Sasai 1, Takeyuki Suzuki 1,*
PMCID: PMC11044153  PMID: 38680320

Abstract

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A practical synthesis of meso-1,4-dialdehydes based on the oxidative cleavage of cyclobutanediol derivatives using polymer-supported periodate was developed. The meso-1,4-dialdehydes were obtained in up to >99% yield and subsequently employed in Ir-catalyzed asymmetric Tishchenko reactions to give the corresponding chiral lactones, which are versatile synthetic intermediates, in good yield with moderate enantiomeric excess. The catalytically active species was identified by means of cold-spray ionization mass spectrometry and 1H NMR spectroscopy.

1. Introduction

The desymmetrization of meso compounds has long been studied in asymmetric synthesis.1−3 Especially, the desymmetrization of prochiral or meso-diols and the corresponding meso-diesters has been intensively investigated, including using enzymatic methods.4,5 In contrast, research on the desymmetrization of prochiral or meso-dialdehydes is relatively scarce, mainly due to problems associated with the stability of the dialdehydes and the immaturity of the synthetic methodology.

In the last four decades, 1,5-prochiral,6−9 1,5-meso-,10−17 1,6-prochiral,18−25 1,6-meso-,26−31 and 1,7-meso-dialdehydes11,15,26,28−30,32 have been synthesized (Figure 1)33 using various methods, including the Swern oxidation of the corresponding diols,11−19,21,22,24 pyridinium-chlorochromate oxidation,32 tetrapropylammonium-perruthenate oxidation,32 oxidative cleavage of diols using H5IO615,26,27,30,31 or NaIO4,6 and ozonolysis of alkenes.8,9,28,29 The purification of 1,7-meso-dialdehydes by column chromatography on silica gel has also been reported,15 albeit that these dialdehydes are generally used without purification. In 1,5-dialdehydes, where the distance between the two formyl groups is shorter, cyclic hydrates are formed.10 In some cases; such cyclic hydrates can be converted to the corresponding dialdehydes by refluxing in tetrahydrofuran (THF) in the presence of 4A molecular sieves.6,9 To avoid hydrate formation in the synthesis of 1,5-dialdehydes, Rein’s method based on Swern oxidation followed by workup under nonaqueous conditions is often used.11

Figure 1.

Figure 1

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Selected Examples of Prochiral or meso-Dialdehydes.

Special 1,4-prochiral dialdehydes such as 1,2-diformylferrocene34−36 can be prepared via oxidation of a dimethylamino group with MnO234,35 or hydrolysis of acetal,36 and these are sufficiently stable to withstand purification by column chromatography on silica gel.35 However, the synthesis of aliphatic 1,4-meso-dialdehydes is not straightforward. For example, although the Pd-catalyzed ambient oxidation of primary alcohols is known to produce aldehydes, the application of these conditions to the reaction of cis-1,2-cyclohexanedimethanol fails to produce the corresponding 1,4-dialdehyde, furnishing instead a five-membered-ring lactone.37 Similarly, the cerium-ammonium-nitrate oxidation of diols with a bicyclo skeleton also produces a five-membered-ring lactone instead of a 1,4-dialdehyde.38 Jacobi has reported the Swern oxidation of 1,2-cyclohexanedimethanol for pyrrole synthesis; however, the stereochemistry of the 1,2-cyclohexanedicarboxaldehyde has not been mentioned.39,40 Bosnich was the first to synthesize 1,2-cyclohexanedicarboxaldehyde from the corresponding amide, albeit that the yield was low (3%) and the aldehyde was obtained as a mixture with an amide-derived byproduct.41

Thus, the challenges associated with the synthesis of aliphatic 1,4-meso-dialdehydes can be summarized as follows: 1) normal oxidation of meso-1,4-diols tends to give lactones; 2) 1,4-meso-dialdehydes are easily epimerized to racemic 1,4-trans-dialdehydes due to the high acidity of the alpha-position of the aldehydes; 3) 1,4-meso-dialdehydes easily form the corresponding cyclic hydrates. Here, we report the first practical method to prepare 1,4-meso-dialdehydes using anhydrous periodate as a heterogeneous oxidant and their application in asymmetric Tishchenko reactions.42−44

2. Results and Discussion

First, we examined the synthesis of meso-cyclohexanedialdehyde from cis-1,2-cyclohexanedimethanol via Swern oxidation, according to Jacobi’s report. Although the 1H NMR spectrum of the product showed only one signal for the aldehydic protons, a careful comparison of the 1H and 13C NMR spectra of the products prepared from cis-1,2-cyclohexanedimethanol or trans-1,2-cyclohexanedimethanol revealed that the product from cis-1,2-cyclohexanedimethanol is a cis:trans = 3.4:1 mixture of 1,2-cyclohexanedicarboxaldehydes, which indicates that epimerization occurred under the basic conditions applied during the triethylamine workup (Scheme 1). It should also be noted that the Swern oxidation of trans-1,2-cyclohexanedimethanol affords the thermally stable trans-1,2-cyclohexanedicarboxaldehyde without epimerization.

Scheme 1. Swern Oxidation of 1,2-Cyclohexanedimethanols.

Scheme 1

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To overcome the epimerization of 1,4-dialdehydes, we attempted the oxidative cleavage of the corresponding 1,2-cyclobutanediols under neutral conditions. Thus, the oxidative cleavage of cyclobutanediols 1a and 1b using silica-gel-supported NaIO4 (SiO2–NaIO4)45 gave the desired meso-dialdehydes 2a and 2b in 60 and 76% yield, respectively, without epimerization (Scheme 2). However, in the case of bicyclic substrates 1c and 1d, the corresponding hydrates 3c and 3d were obtained preferentially, which can be attributed to the shorter distance between the two carbonyl carbons in the bicyclic systems compared to those in the monocyclic systems due to the cyclic strain.

Scheme 2. Oxidative Cleavage Using SiO2-Supported NaIO4.

Scheme 2

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The regeneration of 1,4-dialdehydes 2c and 2d from the corresponding hydrates 3c and 3d was investigated by refluxing in THF in the presence of 4A molecular sieves. After 14 h, the dehydration of 3c proceeded to some extent to give a mixture of dialdehyde 2c (56%) and 3c (44%), whereas the dehydration of 3d did not give the desired product (2d) (Scheme 3).

Scheme 3. Dehydration of Hydrates Using 4A Molecular Sieves.

Scheme 3

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Hodge has developed a polymer-supported periodate, which is prepared using the microporous anion-exchange resin Amberlite IRA 904, for the oxidative cleavage of 1,2-diols.46 In contrast to SiO2–NaIO4, polymer-supported periodate can be used in the dried state; therefore, we envisioned that using the polymer-supported periodate could potentially help to circumvent the hydrate formation, which would provide an effective approach for the synthesis of 1,4-dialdehydes (Table 1).

Table 1. Oxidative Cleavage of Cyclobutanediolsa.

2.

2.

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a

Unless otherwise noted, the reactions were carried out using 0.3–0.4 mmol of 1 with polymer-supported periodate (2 equiv) in CH2Cl2 at 25 °C.

b

1.2 mmol of 1a at 30 °C.

c

Polymer-supported periodate (3 equiv).

d

Determined by 1H NMR spectroscopy.

After screening the reaction conditions (for details, see the Supporting Information), we found that the reactions of 1a and 1b proceeded smoothly to give the desired 1,4-dialdehydes 2a and 2b, respectively, in excellent yield (Table 1, entries 1 and 2). Importantly, the reaction of 1c gave 2c without the formation of hydrate 3c (Table 1, entry 3). The reaction of 1d gave 1,4-dialdehyde 2d in 83% yield, although hydrate 3d was also obtained in 6% yield (Table 1, entry 4). During the oxidative cleavage of 1,2-diol with the polymer-supported periodate, a molecule of H2O was produced (eq 1).47 Therefore, we attempted to obtain pure 2d by adding desiccants such as 3A molecular sieves, CaSO4, K2CO3, or MgSO4 in the reaction of 1d, albeit that no improvement was achieved.

2. 1

With meso-1,4-dialdehydes 2 in hand, we next investigated asymmetric Tishchenko reactions using chiral Ir complexes as catalysts (Table 2). Screening of the chiral ligands and conditions revealed that the catalyst prepared from (1S,2S)-2-amino-1,2-diphenylethanol gave the best results (for details, see the Supporting Information). Treatment of 2a with Ir catalyst 5a (10 mol %) and iPrOH (20 mol %) in the presence of Cs2CO3 (40 mol %) at 25 °C for 3 h provided the desired lactone (4a) in 92% yield with 50% enantiomeric excess (ee) (Table 2, entry 1). The reaction of other 1,4-meso-dialdehydes proceeded with a good yield with moderate ee (Table 2, entries 3–4, 6). The reaction of the mixture of 1,4-dialdehyde 2c and hydrate 3c also proceeded in 64% yield (67% ee) after 10 h, indicating the occurrence of an equilibrium between the 1,4-dialdehyde and the hydrate under the applied reaction conditions. However, the reaction did not reach completion, affording the corresponding lactol in 22% yield together with 3c (14%) (Table 2, entry 5). The reaction of saturated bicyclic 1,4-dialdehydes 2e and 2f proceeded smoothly, albeit with low enantioselectivities (Table 2, entries 7 and 8). These results indicate the double bond might act as a directing group in the case of a conformationally more rigid bicyclic system (entry 4 vs 7, 6 vs 8). This result might be related to the fact that the CH–π interaction has a key role in the chiral recognition of the enantioselective transfer hydrogenation using the arene–metal complex.48 The reaction of 2a with 1 mol % catalyst also proceeded with a 94% yield with 55% ee in a 1 mmol-scale reaction (Table 2, entry 2).

Table 2. Asymmetric Tishchenko Reaction of meso-1,4-Dialdehydesa.

2.

entry substrate time (h) yield (%)b ee (%)c
1 2a 3 92 50
2d 2a 17 94 55
3 2b 2 95 58
4 2c 3 90 61
5 2c + 3c 10 64 67
6 2d 24 91 39
7 2e 3 89 10
8 2f 12 97 2
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a

Unless otherwise noted, the reactions were carried out using 0.25–0.31 mmol of 2 with 5a (10 mol %), iPrOH (20 mol %), and Cs2CO3 (40 mol %) in CH2Cl2/CH3CN = 1/1.

b

Determined by 1H NMR spectroscopy. Isolated yield.

c

Determined by chiral GC.

d

1.0 mmol of 2a with 5a (1 mol %) and iPrOH (2 mol %).

As could be anticipated based on the results of one of our previous studies,42 an enantiodivergent relationship between the asymmetric Tishchenko reaction of meso-1,4-dialdehydes and the asymmetric oxidative lactonization of meso-1,4-diols using the same chiral catalyst was observed. Thus, the asymmetric Tishchenko reaction of meso-1,4-dialdehydes using (S,S)-5a gave (3aS,7aR)-lactones, while the asymmetric oxidative lactonization of meso-1,4-diols gave (3aR,7aS)-lactones (Scheme 4).49

Scheme 4. Asymmetric Tishchenko Reaction and Asymmetric Oxidative Lactonization Catalyzed by an (S,S)-Catalyst.

Scheme 4

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It should also be noted here that the obtained chiral lactones are versatile chiral building blocks. For example, chiral lactone 4a is used for the synthesis of an NMDA antagonist50 and an ACE inhibitor,51 while 4b serves as a starting material for brefeldin A,52 mucosin,53 compactin,54 and aucantene.55 Meanwhile, boschnialactone,56 methyl jasmonate,57 (−)-ngaione,58 and (+)-quercus lactone59 are synthesized from 4c, while differolide60 can be obtained from 4d (Scheme 5).

Scheme 5. Utility of Chiral Lactones.

Scheme 5

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A plausible catalytic cycle for the Ir-catalyzed asymmetric Tishchenko reaction of meso-1,4-dialdehydes is depicted in Scheme 6. Ir complex 5b, which is obtained in situ from 5a, reacts with 2-propanol to give Ir hydride complex 5c. Then, meso-1,4-dialdehyde 2 is reduced by 5c in an enantiotopos-selective manner to give hydroxy aldehyde A, which is in equilibrium with lactol B. Finally, lactol B is oxidized by 5b to give the desired lactone 4, accompanied by the regeneration of the catalyst 5c.

Scheme 6. Plausible Reaction Pathway for the Asymmetric Tishchenko Reaction of meso-1,4-Dialdehydes Catalyzed by a Chiral Ir Complex.

Scheme 6

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The structure of Ir amino alkoxide complexes 5 was examined by means of single-crystal X-ray diffraction analysis, cold-spray ionization mass spectrometry (CSI-MS), and 1H NMR spectroscopy. Figure 2 shows the solid-state structure of iridium complex 5a in the single crystal, where 5a adopts a pseudotetrahedral and three-legged piano stool geometry with Cp*, amino, alkoxide, and chloro ligands. The (S)-configuration around the Ir center stems arises from the chirality of the (S,S)-diphenyl aminoalcohol ligand, which forms a δ-configurated five-membered chelate. The CSI-MS spectra of 5a show the chloride adduct of 5a in negative mode (Figure 3, top). Treatment of 5a with KOH in CH2Cl2 produced 16-electron complex 5b as the chloride adduct (Figure 3, middle). Treatment of 5a with Cs2CO3 in 2-propanol afforded a species with a 2-mass-unit increase, which supports the formation of an Ir hydride complex. All the obtained MS spectra matched the simulated Ir isotope pattern. 1H NMR measurements were carried out to determine the structure of 5a in solution. After treatment of 5a with KOH, all signals shifted, and that corresponding to one of the NH protons disappeared, which supports the formation of 16-electron complex 5b. Further addition of 2-propanol to the reaction mixture resulted in the appearance of a new peak at around −9 ppm, which was attributed to a hydride (for details, see the Supporting Information).

Figure 2.

Figure 2

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Molecular structure of 5a in the single crystal with thermal ellipsoids at 30% probability; all hydrogen atoms, except for the proton of the aminoalcohol ligand and those at the carbon atoms in the chelate backbone, as well as one molecule of water and two molecules of chloroform, are omitted for clarity.

Figure 3.

Figure 3

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Negative CSI-MS spectra of iridium complexes: (top) 5a; (middle) 5b, obtained from treating 5a with KOH in CH2Cl2; and (bottom) 5c, obtained from treating 5a with Cs2CO3 in 2-propanol.

3. Conclusions

In summary, we have developed the first practical method to prepare 1,4-meso-dialdehydes via heterogeneous oxidative cleavage of the corresponding cyclobutanediols using polymer-supported periodate and characterized 1,2-cyclohexanedicarboxaldehyde as one of the simplest 1,4-meso-dialdehydes for the first time. The obtained 1,4-meso-dialdehydes were subsequently employed in asymmetric Tishchenko reactions using a chiral Ir aminoalkoxide complex as the catalyst. This study can be expected to open new synthetic avenues for the desymmetrization of 1,4-meso-dialdehydes.

4. Experimental Section

4.1. General Information

The melting point was measured with the Rigaku TG-DTA Thermo Plus 8120. Infrared (IR) spectra were recorded on a JASCO FT/IR 4100 spectrometer. 1H NMR spectra were recorded on the JEOL JNM-ECS400 NMR, JEOL JNM-ECA600 NMR, or Bruker AVANCE III 700 NMR spectrometer. The chemical shifts are reported in ppm on the δ scale downfield from tetramethylsilane or relative to the residual solvent signals (CDCl3: 7.26 ppm for 1H NMR and 77.16 for 13C{1H} NMR, C6D6: 7.16 ppm for 1H NMR and 128.06 for 13C{1H} NMR, C6D5CD3: 2.08 ppm for 1H NMR and 20.43 for 13C{1H} NMR, CD2Cl2: 5.32 ppm for 1H NMR and 53.84 for 13C{1H} NMR, CD3CN 1.94 ppm for 1H NMR, CD2Cl2: 5.32 ppm for 1H NMR and 53.84 for 13C{1H} NMR, and signal patterns are indicated as follows: s, singlet; d, doublet; t, triplet; m, multiplet; and br, broad peak. 13C{1H} NMR spectra were measured on a JEOL JNM-ECA600 NMR spectrometer at 151 MHz, a Bruker AVANCE III 176 NMR spectrometer at 176 MHz, or a JEOL JNM-ECA400 NMR at 100 MHz. Electrospray ionization (ESI) mass spectra were recorded on a THERMO LTQ Orbitrap XL spectrometer. CSI-MS were recorded on a Bruker micrOTOF II spectrometer with a cryospray unit. X-ray crystallographic analysis was conducted on a Rigaku E-AXIS RAPID 191R diffractometer system equipped with a Rigaku FR-E+2 SuperBright (Cu) X-ray generator or a Rigaku XtaLAB PRO MM007 DW diffractometer system equipped with a MicroMax007HFM-DW(Cu/Mo) X-ray generator and a HyPix-6000HE detector. Optical rotations were measured with a JASCO P-2300 polarimeter. The ee of all the lactones was determined by the Shimazu GC system (GC-2014, AOC-20i autosampler, flame ionization detector): Column: Astec CHIRALDEX G-TA (0.25 mm × 30 m, DF = 0.12 μm). The GC condition: He as a carrier gas, split ratio = 100/1, purge/total flow = 3.0/103.0 mL/min, total pressure: 122.8 kPa, injector and detector temperature = 250 °C, column temperature = 170 °C.

Anhydrous solvents (THF, CH2Cl2, CH3CN, hexane, and toluene from Kanto CHEMICAL Co., INC., Et2O from FUJIFILM Wako Pure Chemical Corp.) were purified by a solvent purification system (GlassContour) equipped with columns of activated alumina prior to use. Other anhydrous solvents, dimethyl sulfoxide (DMSO), MeOH, and EtOH, were purchased from Kanto CHEMICAL Corp. and used without further purification. Amberlite IRA 904Cl (ORGANO.), KOH, Na, NaBH4, Oxalyl chloride (Kishida Chemical), 5% Pd/C (N.E. CHEMCAT), and TMSCl (Tokyo Chemical Industry Co., Ltd. (TCI)), NaIO4, Cs2CO3, 1,4-BTMSB-d4 (FUJIFILM Wako Pure Chemical Corp.) were purchased and used without purification. Silica gel chromatography was performed using 40–50 μm Kanto (silica gel 60N, spherical, neutral). Cis- or trans-cyclohexanedimethanol,61 (1S,2S)-2-amino-1,2-diphenylethan-1-ol62 was prepared according to the literature.

4.1.1. (Scheme 1) Swern Oxidation of 1,2-Cyclohexanedimethanols

(aqueous workup using cis-diol)

Oxalyl chloride (0.156 mL, 1.80 mmol) was added dropwise to the DMSO (0.260 mL, 3.68 mmol) in CH2Cl2 solution (12 mL) at −78 °C and stirred for 1 h. cis-1,2-Cyclohexanedimethanol (100 mg, 0.693 mmol) in CH2Cl2 (4 mL) was added dropwise and stirred for 2 h. Triethylamine (0.967 mL, 6.93 mmol) was added at −78 °C, and then the reaction mixture was warmed up to an ambient temperature and stirred for 12 h. The reaction mixture was washed with 1 M aq HCl, sat. NaHCO3, brine, dried over Mg2SO4, and filtrated. The filtrate was evaporated under reduced pressure. The crude mixture was purified with a silica gel column (ethyl acetate) to give the dialdehyde as a diastereo mixture (57.6 mg, 59%, cis/trans = 3.4:1).

4.1.2. (Nonaqueous Workup Using cis-Diol)

Oxalyl chloride (0.160 mL, 1.85 mmol) was added dropwise to the DMSO (0.260 mL, 3.68 mmol) in CH2Cl2 solution (30 mL) at −78 °C. cis-1,2-Cyclohexanedimethanol (102 mg, 0.707 mmol) in CH2Cl2 (4 mL) was added dropwise and stirred for 13 h. Triethylamine (1.00 mL, 7.17 mmol) was added at −78 °C, and then the reaction mixture was warmed up to an ambient temperature and stirred for 9 h. The reaction mixture was filtrated with a Celite pad and washed with hexane–toluene 1:1. The filtrate was evaporated under reduced pressure. The crude mixture was purified with a silica gel column (ethyl acetate) to give the dialdehyde as a diastereo mixture (81.2 mg, 82%, cis/trans = 4.8:1).

4.1.3. (Aqueous Workup Using trans-diol)

Oxalyl chloride (0.156 mL, 1.80 mmol) was added dropwise to the DMSO (0.256 mL, 3.61 mmol) in CH2Cl2 solution (12 mL) at −78 °C and stirred for 20 min. trans-1,2-Cyclohexanedimethanol (100 mg, 0.693 mmol) in CH2Cl2 (4 mL) was added dropwise and stirred for 3 h. Triethylamine (0.967 mL, 6.93 mmol) was added at −78 °C, and then the reaction mixture was warmed up to an ambient temperature and stirred overnight. The reaction mixture was washed with brine, dried over Na2SO4, and filtrated. The filtrate was evaporated under reduced pressure. The crude mixture was purified with a silica gel column (ethyl acetate) to give the dialdehyde as a single diastereomer (72.2 mg, 74%, cis/trans = 0:1).

4.1.4. trans-Cyclohexane-1,2-dicarbaldehyde (trans-2a)63,64 Purple Color Oil (72.2 mg, 74%)

1H NMR (600 MHz, CDCl3): δ 9.71(s, 2H), 2.70–2.68(m, 2H), 2.08–2.05(m, 2H), 1.79–1.77(m, 2H), 1.37–1.25(m, 4H); 13C{1H} NMR(151 MHz, CDCl3): 202.9(2C), 49.2(2C), 24.95(2C), 24.86(2C); ESI-HRMS: calcd for C8H12O2Na, 163.0730(M + Na+); found, 163.0729; IR(KBr): 2928, 1727 cm–1

4.2. General Procedure for the Synthesis of Cyclobutandiols

The cis-cyclobutanediol derivatives were prepared by Hartmann’s procedure.64

Starting from the corresponding methyl ester, the acyloin condensation (step 1) afforded cyclobutane acyloin in 83–95% yield. After sodium borohydride reduction (step 2), 1,2-cyclobutane diol is obtained in 35–75%.

4.2.1. (1R*,6S*,7S*,8R*)-Bicyclo[4.2.0]octane-7,8-diol (1a)65 (Step1:83%, Step2:51%)

1H NMR(600 MHz, CDCl3): δ 4.31 (t, J = 4.1 Hz, 2H), 2.34–2.31 (m, 4H), 1.70–1.68 (m, 2H), 1.64–1.52 (m, 4H), 1.34–1.29 (m, 2H); 13C{1H} NMR(151 MHz, CDCl3)δ: 71.3(2C), 34.7(2C), 22.8(2C), 21.3(2C); ESI-HRMS: calcd for C8H14O2Na (M + Na+), 165.0886; found, 165.0884; IR(KBr): 3445, 3369, 2934 cm–1; mp 70.1 °C.

4.2.2. (1R*,6S*,7S*,8R*)-Bicyclo[4.2.0]oct-3-ene-7,8-diol (1b)66 (Step1:81%, Step2:35%)

1H NMR (600 MHz, CDCl3): δ 5.98 (t, J = 1.2 Hz, 2H), 4.35 (s, 2H), 2.73–2.70 (m, 2H), 2.37 (s, 2H), 2.25–2.20 (m, 2H), 2.05–2.02 (m, 2H); 13C{1H} NMR(151 MHz, CDCl3): 128.4(2C), 69.7(2C), 33.5(2C), 19.6(2C); ESI-HRMS: calcd for C8H12O2Na (M + Na+), 163.0730; found, 163.0728; IR(KBr): 3367, 3040, 2940 cm–1; mp 60.4 °C.

4.2.3. (1R*,2S*,3S*,4R*,5R*,6S*)-Tricyclo[4.2.1.02,5]-7-nonene-3,4-diol (1c)67 (Step1:82%, Step2:38%)

1H NMR (600 MHz, CDCl3): δ 6.32 (t, J = 1.7 Hz, 2H), 4.28 (d, J = 4.1 Hz, 2H), 2.97 (d, J = 1.4 Hz, 2H), 2.92–2.89 (m, 2H), 1.91 (br s, 2H), 1.39 (d, J = 8.2 Hz, 1H), 1.02 (d, J = 8.2 Hz, 1H); 13C{1H} NMR(150 MHz,CDCl3):137.0(2C), 68.9(2C), 53.3, 45.8(2C), 44.8(2C); ESI-HRMS: calcd for C9H12O2Na (M + Na+), 175.0730; found, 175.0727; IR(KBr): 3361, 3077 cm–1; mp 106.5 °C.

4.2.4. (1R*,2S*,3S*,4R*,5R*,6S*)-Tricyclo[4.2.2.02,5]-7-decene-3,4-diol (1d)68 (Step1:95%, Step2:75%)

1H NMR (400 MHz, CDCl3): δ 6.50 (dd, J = 4.6, 3.2 Hz, 2H), 4.38–4.34 (m, 2H), 2.72–2.69 (m, 4H), 2.16 (d, J = 8.2 Hz, 2H), 1.44–1.41 (m, 2H), 1.25–1.21 (m, 2H); 13C{1H} NMR(151 MHz, CDCl3):135.3(2C), 70.1(2C), 45.8(2C), 29.4(2C), 24. 5(2C); ESI-HRMS: Calcd for C10H14O2Na(M + Na+), 189.0886; found, 189.0887; IR(KBr): 3505, 3367, 2950 cm–1; mp 100.6 °C.

4.2.5. (1R*,2R*,3R*,4S*,5S*,6S*)-Tricyclo[4.2.1.02,5]nonane-3,4-diol (1e)

Hydrogenation of 1c (109 mg, 0.716 mmol) using 5% Pd/C (76.2 mg, 0.0716 mmol, 10 mol %) in EtOH (2.4 mL) under H2 atmosphere (1 atm) at 25 °C for 2 h gave 1e (108 mg, 98%).

1H NMR (600 MHz, CDCl3): δ 4.54 (d, J = 5.2 Hz, 2H), 2.56–2.54 (m, 2H), 2.50–2.48 (m, 2H), 2.41–2.39 (m, 2H), 2.27 (br s, 2H), 1.45–1.43 (m, 2H), 1.27 (dt, J = 9.3, 1.4 Hz, 1H), 1.12–1.10 (m, 1H); 13C{1H} NMR(150 MHz, CDCl3): δ 69.9(2C), 43.8(2C), 43.2, 40.9(2C), 25.1(2C); ESI-HRMS: calcd for C9H14O2Na(M + Na+), 177.0886; found, 177.0883; IR(KBr): 3380, 2924 cm–1; mp 92.1 °C.

4.2.6. (2S*,3S*,4R*,5R*)-Tricyclo[4.2.2.02,5]decane-3,4-diol (1f)

Hydrogenation of 1d (101 mg, 0.606 mmol) using 5% Pd/C (64.5 mg, 0.030 mmol, 5 mol %) in EtOH (25 mL) under H2 atmosphere (1 atm) at 30 °C for 12 h gave 1f (91.8 mg, 90%).

1H NMR (600 MHz, CDCl3): δ 4.63 (dd, J = 5.2, 4.1 Hz, 2H), 2.41–2.40 (m, 2H), 2.28–2.26 (m, 2H), 1.77–1.76 (m, 2H), 1.59–1.55 (m, 2H), 1.47 (dd, J = 11.9, 4.6 Hz, 2H), 1.39–1.35 (m, 2H); 13C{1H} NMR (151 MHz, CDCl3): 71.4(2C), 40.9(2C), 27.2(2C), 24.2(2C), 23.6(2C); ESI-HRMS: calcd for C10H16O2Na(M + Na+), 191.1043; found, 191.1040; IR(KBr): 3352, 2927 cm–1; mp 89.5 °C.

4.3. (Scheme 2) General Procedure for Oxidative Cleavage by Silica Gel-Supported NaIO4

To a vigorously stirred suspension of silica gel-supported NaIO4 reagent45 (2 equiv) in a 10 mL test tube was added a solution of diol (0.9 mmol) in CH2Cl2 (0.1 M) at 30 °C. The reaction was monitored by TLC until the disappearance of the starting material (generally 10–30 min). The mixture was filtered through a sintered glass funnel, and the silica gel was thoroughly washed with CHCl3 (3 × 10 mL). Removal of solvents from the filtrate afforded aldehyde that was pure enough for most purposes. The chemical yield was estimated using 1,1,2,2-tetrachloroethane as an internal standard.

4.4. (Scheme 3) Dehydration of Hydrate by MS 4A

The hydrate 3c (34.2 mg, 0.206 mmol) in THF (5 mL) was refluxed for 14 h using Dean–Stark with MS4A. After cooling the reaction mixture, the solution was evaporated under reduced pressure, and the crude material was subjected to NMR measurement.

4.5. Preparation of Resin-IO446

Amberlite IRA904-Cl (ORGANO corp., 25 g) was added into a 500 mL Erlenmeyer flask that contains fresh NaIO4 aqueous solution (20.0 g, 93.5 mmol) in deionized water (200 mL) on the shaker (EYELA MRM-1000). After shaking (shaking speed: 100 rpm, tilt angle: 3°, mode: reciprocation and vibration) at room temperature for 6 h, the solution part was decanted off, and the solid part was again treated with a fresh NaIO4 solution (20.0 g in 200 mL). After further shaking for 7 h, the resulting mixture was filtered and washed with water (100 mL), THF (100 mL), and Et2O (100 mL) and dried in the vacuum at 40 °C overnight. The effective weight percentage of the resulting periodate resin was determined by iodometry using aq. 0.005 M aq. Na2SO3 solution. Normally, this procedure provides the resin product containing 0.10–0.24 mmol of periodate anion per gram.

4.6. General Procedure for Oxidative Cleavage by Resin-IO4 Oxidative Cleavage

To a 0.075–0.09 M solution of diol 1 in CH2Cl2 was added resin periodate (2–3 equiv), and the reaction mixture was stirred at 25 °C. The reaction was monitored by TLC until the disappearance of the starting material. The mixture was filtered through a poly(tetrafluoroethylene) (PTFE) membrane, washed with CH2Cl2 (3 × 4 mL), and evaporated under reduced pressure to give the dialdehyde. In the case of meso-dialdehyde 2c–2f, which is aerobically unstable, the chemical yield was determined using 1,4-BTMSB-d4 as an internal standard. The filtered solution of 2c–2f was concentrated to the suitable concentration and used as a solution for the following asymmetric Tishchenko reaction.

4.6.1. cis-Cyclohexane-1,2-dicarbaldehyde (cis-2a)41

(Yellow oil: 98.8 mg, 99%: from 0.09 M of 1a (0.713 mmol), 30 °C, 2 h) 1H NMR (600 MHz, CDCl3): δ 9.70 (s, 2H), 2.71 (brm, 2H), 1.96 (brm, 2H), 1.89–1.82 (m, 2H), 1.49 (brm, 4H); 1H NMR (700 MHz, C6D6): δ 9.29 (s, 2H), 1.91 (brm, 2H), 1.50 (ddd, 2H), 1.25 (brm, 2H), 1.02 (brm, 2H), 0.96–0.93 (m, 2H); 13C{1H} NMR(151 MHz, CDCl3): 203.5(2C), 48.9(2C), 24.1(4C); 13C{1H} NMR(176 MHz, C6D6): 202.0(2C), 48.6(2C), 24.1(2C), 24.0(2C); ESI-HRMS: calcd for C8H12O2Na (M + Na+), 163.0730(M + Na+); found, 163.0729; IR(KBr): 2931, 1721 cm–1.

4.6.2. mmol Scale Reaction of Oxidative Cleavage by Resin-IO4 of 1a

To a solution of diol 1a (171 mg, 1.20 mmol) in CH2Cl2 (12 mL) in a 30 mL round-bottom flask was added 25% resin periodate (1.837 g, 2 equiv), and the reaction mixture was stirred at 30 °C for 1 h. The mixture was filtered through a PTFE membrane, washed with CH2Cl2 (3 × 5 mL), and evaporated under reduced pressure to give the dialdehyde (168 mg, >99%) as a yellow oil.

4.6.3. cis-4-Cyclohexene-1,2-dicarbaldehyde (cis-2b)69

(Yellow liquid: 41.3 mg, 99%: from 0.075 M of 1b (0.299 mmol) 1 H NMR(600 MHz, CDCl3): δ 9.71 (s, 2H), 5.75 (t, J = 1.4 Hz, 2H), 2.92–2.90 (m, 2H), 2.52–2.49 (m, 2H), 2.43–2.40 (m, 2H); 13C{1H} NMR(151 MHz, CDCl3): δ 202.9(2C), 125.8(2C), 45.8(2C), 23.7(2C); ESI-HRMS: calcd for C8H10O2Na(M + Na+), 161.0573; found, 161.0574; IR(KBr): 3023, 2910, 1722, 1660 cm–1

4.6.4. (1R*,2S*,3R*,4S*)-Bicyclo[2.2.1]-5-heptene-2,3-dicarbaldehyde (cis-2c)70

(91%, NMR yield: from 0.075 M of 1c (0.302 mmol) 1H NMR (600 MHz, CDCl3): δ: 9.53 (s, 2H), 6.31 (t, J = 1.7 Hz, 2H), 3.33 (dq, J = 9.5, 2.4 Hz, 4H), 1.60 (dt, J = 8.7, 1.7 Hz, 1H), 1.45 (d, J = 8.9 Hz, 1H); 13C{1H} NMR: δ = 201.6, 135.6, 58.2, 49.4, 45.7.

ESI-HRMS: calcd for C9H10O2Na+(M + Na+), 173.0573; found, 173.0572; IR(KBr): 2941, 1727 cm–1

4.6.5. (1R*,2S*,3R*,4S*)-Bicyclo[2.2.2]-5-octene-2,3-dicarbaldehyde (cis-2d)70

(83%, NMR yield: from 0.09 M of 1d (0.367 mmol) 1H NMR (400 MHz, CD2Cl2): δ 9.49 (s, 2H), 6.34 (dd, J = 4.6, 3.2 Hz, 2H), 3.03–2.98 (m, 4H), 1.69–1.62 (m, 2H), 1.40–1.36 (m, 2H); 13C{1H} NMR (151 MHz, CDCl3): δ 201.4, 133.6, 56.4, 31.2, 24.8; ESI-HRMS: calcd for C10H12O2Na+(M + Na+), 187.0730; found, 187.0730; IR(KBr): 2943, 1720 cm–1

4.6.6. Bicyclo[2.2.2]octa-2,5-diene-2,3-dicarbaldehyde (2d′)71

(4%, determined by NMR using 1,4-BTMSB-d4 as an internal standard)

1H NMR (700 MHz, CDCl3): δ 10.52 (s, 2H), 6.39 (dd, J = 4.4, 3.1 Hz, 2H), 4.44–4.43 (m, 2H), 1.48–1.47 (m, 2H), 1.34–1.33 (m, 2H); 13C{1H} NMR (176 MHz, CDCl3): δ 185.8(2C), 154.6(2C), 133.8(2C), 34.8(2C), 24.4(2C); ESI-HRMS: calcd for C10H11O2 (M + H+), 163.0754; found, 163.0729; IR(KBr) 2943, 1716, 1665 cm–1.

4.6.7. (1R*,2S*,3R*,4S*)-Bicyclo[2.2.1]-5-heptane-2,3-dicarbaldehyde (cis-2e)70

(98%, NMR yield: from 0.0785 M of 1e (0.314 mmol) 1H NMR(600 MHz, CDCl3): δ 9.83 (s, 2H), 2.98–2.97 (br m, 2H), 2.78–2.77 (m, 2H), 1.60–1.52 (m, 6H); 13C{1H} NMR (151 MHz, CDCl3): δ: 202.0(2C), 55.2(2C), 40.0, 39.4(2C), 34.8(2C), 24.1(2C); ESI-HRMS: calcd for C9H12O2Na+(M + Na+), 175.0730; found, 175.0728; IR(KBr): 2941, 1727 cm–1.

4.6.8. (1R*,2S*,3R*,4S*)-Bicyclo[2.2.2]-5-octane-2,3-dicarbaldehyde (cis-2f)70

(94%, NMR yield: from 0.075 M of 1f (0.303 mmol) 1H NMR (600 MHz, CDCl3): δ 9.80 (s, 2H), 2.85 (s, 2H), 2.23 (s, 2H), 1.68–1.55 (m, 8H); 13C{1H} NMR: δ 202.2(2C), 51.6(2C), 25.8(2C), 25.2(2C), 21.4(2C); IR(KBr): 2943, 1722 cm–1; ESI-HRMS: calcd for C10H14O2Na+(M + Na+), 189.0886; found, 189.0884.

4.6.9. (3aR*,4S*,7R*,7aS*)-1,3,3a,4,7,7a-Hexahydro-4,7-methanoisobenzofuran-1,3-diol (3c)72

1H NMR (400 MHz, CDCl3): δ 6.09 (t, J = 1.8 Hz, 2H), 4.96–4.87 (m, 2H), 3.35 (br s, 1H), 3.03–2.99 (m, 4H), 1.67–1.65 (br s, 1H), 1.44 (d, J = 8.2 Hz, 1H), 1.32 (d, J = 8.2 Hz, 1H).

13C{1H} NMR (100 MHz, CDCl3): δ 134.5 (2C), 102.4 (2C), 54.9 (2C), 51.5, 45.0 (2C).

4.6.10. (3aR*,4S*,7R*,7aS*)-1,3,3a,4,7,7a-Hexahydro-4,7-ethanoisobenzofuran-1,3-diol (3d)

1H NMR (400 MHz, CDCl3): δ 6.17 (dd, J = 4.8, 3.4 Hz, 2H), 5.07 (s, 2H), 3.91 (br s, 2H), 2.75–2.73 (br m, 2H), 2.54 (s, 2H), 1.51–1.49 (m, 2H), 1.24–1.20 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3): δ: 132.9(2C), 105.3(2C), 52.8(2C), 32.3(2C), 24.2(2C).

ESI-HRMS: calcd for C10H14O3Na+, 205.0835 (M + Na+); found, 205.0835; IR(KBr): 3387, 3270, 2938 cm–1; mp 100.8 °C.

4.7. General Procedure of the Asymmetric Tishchenko Reaction

The reactions were performed using an EYELA personal organic synthesizer, ChemiStation PPS-5511. To a 10 mL Schlenk tube, including Ir complex 5a (10 mol %) and Cs2CO3 (40 mol %) was added a 0.1 M solution of 2-propanol in CH3CN (20 mol %) and stirred for 10 min. Then CH3CN and a solution of meso-2 in CH2Cl2 were added and stirred at 25 °C. Without special mention, the reaction was performed with CH3CN/CH2Cl2 = 1:1 as a solvent, 0.05 molar, based on the starting material. The mixture was passed through a short silica gel column (ethyl acetate) to remove the catalyst and concentrated under reduced pressure. Then, the crude mixture was analyzed by quantitative NMR using 1,4-bis(trimethylsilyl)benzene-d4 (1,4-BTMSB-d4) as an internal standard and purified by silica gel column chromatography (hexane/ethyl acetate = 90/10) to give lactone 4. The ee of all the lactones was determined by a chiral GC analysis: Column: Astec CHIRALDEX G-TA (0.25 mm × 30 m, DF = 0.12 μm) Condition: He as a carrier gas, split ratio = 100/1, purge/total flow = 3.0/103.0 mL/min, total pressure: 122.8 kPa, injector and detector temperature = 250 °C, column temperature = 170 °C.

4.8. Procedure of 1 mmol Scale Asymmetric Tishchenko Reaction of cis-2a with 1 mol % Catalyst-Loading

To a 10 mL Schlenk tube, including Ir complex 5a (6.0 mg, 0.01 mmol, 1 mol %) and Cs2CO3 (135.5 mg, 0.416 mmol, 40 mol %) was added a 0.1 M solution of 2-propanol in CH3CN 0.2 mL (0.02 mmol, 2 mol %) and stirred for 10 min. Then CH3CN (5.0 mL) and a solution of cis-2a (145.7 mg, 1.039 mmol) in CH2Cl2 (5.2 mL) were added and stirred at 25 °C for 17 h. The mixture was passed through a short silica gel column (ethyl acetate) to remove the catalyst and concentrated under reduced pressure. Then, the crude mixture was analyzed by quantitative NMR using 1,4-BTMSB-d4 as an internal standard (94% yield) and purified by silica gel column chromatography (hexane/ethyl acetate = 9/1) to give the lactone 4a as a colorless oil (120.8 mg, 83%, 55% ee).

4.8.1. (3aR, 7aS)-Hexahydroisobenzofuran-1(3H)-one (4a)73 120.8 mg, Colorless Oil, 94%, 55 ee

1H NMR (600 MHz, CDCl3): δ 4.20 (dd, J = 8.8, 5.0 Hz, 1H), 3.96 (dd, J = 8.8, 1.3 Hz, 1H), 2.65 (td, J = 5.2, 2.8 Hz, 1H), 2.47–2.46 (m, 1H), 2.13–2.10 (m, 1H), 1.84–1.81 (m, 1H), 1.66–1.62 (m, 3H), 1.28–1.17 (m, 3H); 13C{1H} NMR (151 MHz, CDCl3): δ 178.7, 71.9, 39.6, 35.5, 27.3, 23.6, 23.1, 22.6; [α]D25 = +26.9° (c 0.5, CHCl3, 55% ee). lit. [α]D25 = +48.8° (c 0.5, CHCl3, >99% ee);61 Retention time: 8.5 min (3aS, 7aR), 8.8 min (3aR, 7aS).

4.8.2. (3aR, 7aS)-3a,4,7,7a-Tetrahydroisobenzofuran-1(3H)-one (4b)74

White solid, 95%, 59% ee. 1H NMR (600 MHz, CDCl3): δ 5.75–5.75 (m, 2H), 4.32 (dd, J = 8.8, 5.2 Hz, 1H), 4.04 (dd, J = 8.8, 2.1 Hz, 1H), 2.79–2.78 (m, 1H), 2.66–2.61 (m, 1H), 2.53–2.50 (m, 1H), 2.42–2.36 (m, 1H), 2.29–2.27 (m, 1H), 1.95–1.89 (m, 1H); 13C{1H} NMR (151 MHz, CDCl3): δ 179.2, 125.3124.9, 72.8, 37.4, 32.1, 24.8, 22.1; [α]D25 = −27.1° (c 1.0, CHCl3, 59% ee). lit. [α]Drt = +46.7° (c 1.0, CHCl3, >99% ee).75 Retention time: 9.3 min (3aS, 7aR), 9.7 min (3aR, 7aS).

4.8.3. (3aR, 4S,7R,7aS)-3a,4,7,7a-Tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (4c)74

White solid, 90%, 61% ee. 1H NMR (600 MHz, CDCl3): δ 6.31 (dd, J = 5.8, 2.9 Hz, 1H), 6.28 (dd, J = 5.8, 2.4 Hz, 1H), 4.29 (dd, J = 9.8, 8.5 Hz, 1H), 3.80 (dd, J = 9.8, 3.2 Hz, 1H), 3.36–3.34 (m, 1H), 3.26–3.25 (m, 1H), 3.11–3.10 (m, 2H), 1.65 (dt, J = 8.6, 1.5 Hz, 1H), 1.47 (d, J = 8.6 Hz, 1H); 13C{1H} NMR (151 MHz, CDCl3): δ 178.2, 137.1, 134.5, 70.4, 52.0, 47.7, 46.3, 45.9, 40.4; [α]D25 = +88.9° (c 1.0, CHCl3, 61% ee). lit. [α]D20 = −147.8° (c 1.0, CHCl3, >99% ee);76 Retention time: 15.6 min (3aR, 4S, 7R, 7aS), 16.9 min (3aS, 4R, 7S, 7aR).

4.8.4. (3aR, 4S, 7R, 7aS)-3a,4,7,7a-Tetrahydro-4,7-ethanoisobenzofuran-1(3H)-one (4d)74

White solid, 91%, 39% ee. 1H NMR (600 MHz, CDCl3): δ 6.34 (t, J = 6.9 Hz, 1H), 6.28 (t, J = 7.2 Hz, 1H), 4.35 (t, J = 9.3 Hz, 1H), 3.85 (dd, J = 9.3, 3.8 Hz, 1H), 3.09–3.08 (m, 1H), 2.77 (dd, J = 10.3, 3.4 Hz, 1H), 2.72–2.71 (m, 2H), 1.59–1.57 (m, 1H), 1.51–1.49 (m, 1H), 1.37–1.27 (m, 2H); 13C{1H} NMR (151 MHz, CDCl3): δ 179.5, 134.4, 132.8, 72.5, 44.9, 38.1, 33.5, 31.8, 23.6, 23.5; [α]D25 = +30.4° (c 0.5, CHCl3, 39%ee). lit. [α]D25 = −86.8° (c 0.5, CHCl3, >95% ee);77 Retention time: 26.2 min (3aR, 4S, 7R, 7aS), 29.0 min (3aS, 4R, 7S, 7aR).

4.8.5. (3aR,4R,7S,7aS)-Hexahydro-4,7-methanoisobenzofuran-1(3H)-one (4e)78

White solid, 89%, 10%ee. 1H NMR (700 MHz, CDCl3): δ 4.30 (dd, J = 10.0, 8.4 Hz, 1H), 4.25 (dd, J = 10.1, 2.8 Hz, 1H), 2.98 (ddd, J = 11.4, 5.6, 1.5 Hz, 1H), 2.88–2.86 (m, 1H), 2.67–2.66 (m, 1H), 2.37–2.37 (brm, 1H), 1.61–1.48 (m, 6H); 13C{1H} NMR (176 MHz, CDCl3): δ 179.0, 68.6, 46.9, 42.12, 42.0, 40.5, 40.0, 25.6, 21.7; [α]D25 = +15.1 (c 0.84, CHCl3). lit. [α]D29 = −145.4°(c 1.0, CHCl3, >95% ee) (3aS,4S,7R,7aR).79

4.8.6. (3aR,7aS)-Hexahydro-4,7-ethanoisobenzofuran-1(3H)-one (4f)80

White solid, 97%, 2%ee. 1H NMR (700 MHz, CDCl3): δ 4.46 (dd, J = 9.6, 8.9 Hz, 1H), 4.21 (dd, J = 9.6, 3.3 Hz, 1H), 2.71–2.63 (m, 2H), 2.07–2.07 (m, 1H), 1.73–1.41 (m, 9H); 13C{1H} NMR (176 MHz, CDCl3): δ 180.2, 71.1, 41.9, 36.3, 27.2, 25.8, 25.0, 24.6, 21.7, 19.8.

4.8.7. Preparation of Iridium Catalyst 5a

To a solution of [Cp*IrCl2]2 (500 mg, 0.628 mmol), (1S, 2S)-2-amino-1,2-diphenylethan-1-ol61 (268 mg, 1.26 mmol) in CH2Cl2 (12 mL) was added dropwise triethylamine (0.35 mL, 2.51 mmol) at 30 °C and stirred for 1 h. The resulting yellow solution was washed with H2O (12 mL) twice, washed with brine, and dried with anhydrous Na2SO4. After filtration and evaporation, the reaction afforded 677 mg (93%) as a yellow solid.

4.8.7.1. (1S,2S)-Cp*Ir[NH2CHPhCHPhO]Cl-5a81

1H NMR (700 MHz, CD2Cl2): δ 7.24–7.19 (m, 3H), 7.08–7.07 (m, 3H), 7.05–7.03 (m, 4H), 4.72 (d, J = 9.9 Hz, 1H), 4.49 (d, J = 6.2 Hz, 1H), 4.26 (t, J = 10.9 Hz, 1H), 3.18 (br s, 1H), 1.74 (s, 15H); 13C{1H} NMR (176 MHz, CD2Cl2): δ 144.0, 139.6, 128.9(2C), 128.3, 127.77(2C), 127.73(2C), 127.69(2C), 127.0, 85.2, 83.2(5C), 73.0, 9.0(5C); IR(KBr)3209, 2920, 1493, 1452, 1380, 1026, 700, 581 cm–1; [α]D25 = −73.0° (c 0.5, CHCl3, >99% ee).

4.8.7.2. (1S,2S)-Cp*Ir[NHCHPhCHPhO]-5b

KOH (9.76 mg, 0.174 mmol, 10 equiv) was added to a solution of 5a (10.0 mg, 0.0174 mmol) in degassed toluene-d8 (0.5 mL) on an NMR tube under an Ar stream and sonicated for 45 min before the NMR experiment. During the sonication, the color of the reaction mixture was changed from yellow to red.

1H NMR (700 MHz, C6D5CD3): δ 7.39 (d, J = 7.5 Hz, 2H), 7.26 (d, J = 7.3 Hz, 2H), 7.12–7.11 (m, 3H), 7.08–7.03 (m, 3H), 5.31 (br s, 1H), 4.84 (d, J = 8.2 Hz, 1H), 4.36 (br s, 1H), 1.61 (s, 15H); 13C{1H} NMR (176 MHz, C6D5CD3): δ 147.1, 146.1, 92.7, 83.2, 82.4(5C), 9.9(5C). (Other benzene ring carbons are overlapping with the NMR solvent.)

4.8.7.3. (1S,2S)-Cp*Ir[NHCHPhCHPhO]-5c

KOH (9.76 mg, 0.174 mmol, 10 equiv) was added to a solution of 5a (10.0 mg, 0.0174 mmol) in degassed CD3CN (0.5 mL) on an NMR tube under an Ar stream and sonicated for 45 min before the NMR experiment. During the sonication, the color of the reaction mixture was changed from yellow to red. After confirming the disappearance of 5a by NMR measurement, 2-PrOH (0.1 mL, 1.30 mmol, 75 equiv) was added and mixed with a vortex mixer for 10 min before NMR measurement.

1H NMR (600 MHz, CD3CN): δ 7.06–7.01 (m, 10H), 4.78 (br s, 1H), 4.69 (br s, 1H), 4.00 (d, J = 9.6 Hz, 1H), 3.17–3.15 (brm, 1H), 1.84 (s, 15H), -9.26 (s, 1H).

Acknowledgments

This work was supported by JSPS KAKENHI grants 26410047, 17K05784, and 20K05494, as well as by the Uehara Memorial Foundation and the Fugaku Trust for Medicinal Research. This work was also supported in part by a “Network Joint Research Center for Materials and Devices” grant (20194015) from the “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” program of the Japanese Ministry of Education, Culture, Sports, Science, and Technology (MEXT). The authors would also like to gratefully acknowledge the assistance of Tsuyoshi Matsuzaki, Hitoshi Haneoka, Tsunayoshi Takehara, and Yosuke Murakami of the Comprehensive Analysis Center of SANKEN.

Data Availability Statement

The data underlying this study are available in the published article and its online Supporting Information.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.3c09381.

  • (CIF)

  • (CIF)

  • (CIF)

  • (CIF)

  • Experimental details, characterization data, and copies of the 1H and 13C NMR spectra (PDF)

Author Present Address

† Department of Chemistry, Diponegoro University, Tembalang Semarang – 50275, Center of Java, Indonesia

The authors declare no competing financial interest.

Supplementary Material

ao3c09381_si_001.cif (411.9KB, cif)
ao3c09381_si_002.cif (350.2KB, cif)
ao3c09381_si_003.cif (514.4KB, cif)
ao3c09381_si_004.cif (1.6MB, cif)
ao3c09381_si_005.pdf (2MB, pdf)

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

ao3c09381_si_001.cif (411.9KB, cif)
ao3c09381_si_002.cif (350.2KB, cif)
ao3c09381_si_003.cif (514.4KB, cif)
ao3c09381_si_004.cif (1.6MB, cif)
ao3c09381_si_005.pdf (2MB, pdf)

Data Availability Statement

The data underlying this study are available in the published article and its online Supporting Information.

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