Enantiodifferentiating Photocyclodimerization of 2 ... - ACS Publications


Sep 11, 2012 - ... and 2-anthracenecarboxylic acid (AC) mediated by a chiral hydrogen-bonding template (TKS) was investigated under various conditions...
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ORGANIC LETTERS

Enantiodifferentiating Photocyclodimerization of 2‑Anthracenecarboxylic Acid via Competitive Binary/Ternary Hydrogen-Bonded Complexes with 4‑Benzamidoprolinol

2012 Vol. 14, No. 18 4962–4965

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Yuko Kawanami,† Shin-ya Katsumata,† Jun-ichi Mizoguchi,§ Masaki Nishijima,‡ Gaku Fukuhara,† Cheng Yang,†, Tadashi Mori,† and Yoshihisa Inoue*,† Department of Applied Chemistry and Office for University-Industry Collaboration, Osaka University, 2-1 Yamadaoka, Suita 565-0871, Japan, Bio/Fine Chemicals Department, Nagase ChemteX, 2-2-3 Murotani, Nishi-ku, Kobe 651-2241, Japan, and College of Chemistry, Sichuan University, Wangjiang Road, Chengdu 610064, China [email protected] Received August 22, 2012

ABSTRACT

Circular dichroism (CD) spectral examinations at various host/guest ratios revealed that 2-anthracenecarboxylic acid (AC) forms not only 1:1 but also novel 2:1 hydrogen-bonded/π-stacked complexes with a chiral 4-benzamidoprolinol template (TKS159). The 2:1 complexation is a minor process but causes significant CD spectral changes as a consequence of the exciton coupling interaction of two AC chromophores and greatly accelerates the head-to-head photocyclodimerization to significantly affect the stereochemical outcomes.

Of several photochemical approaches to asymmetric synthesis, supramolecular photochirogenesis is of particular interest and has attracted much attention in recent †

Department of Applied Chemistry, Osaka University. Nagase ChemteX. ‡ Office for University-Industry Collaboration, Osaka University. Sichuan University. (1) (a) Griesbeck, A. G.; Meierhenrich, U. J. Angew. Chem., Int. Ed. 2002, 41, 3147. (b) Inoue, Y.; Ramamurthy, V., Eds. Chiral Photochemistry; Marcel Dekker: New York, 2004. (c) M€uller, C.; Bach, T. Aust. J. Chem. 2008, 61, 557. (d) Hoffmann, N. Chem. Rev. 2008, 108, 1052. (e) Ramamurthy, V., Inoue, Y., Eds. Supramolecular Photochemistry; Hoboken, NJ: Wiley; 2011. )

§

10.1021/ol3023402 r 2012 American Chemical Society Published on Web 09/11/2012

years.1 Thus, chiral supramolecular hosts, such as chirally modified zeolites,2 cyclodextrins,3 and proteins,4 have been employed to confine prochiral substrate(s) in their chiral (2) (a) Joy, A.; Scheffer, J. R.; Ramamurthy, V. Org. Lett. 2000, 2, 119. (b) Sivaguru, J.; Natarajan, A.; Kaanumalle, L. S.; Shailaja, J .; Uppili, S.; Joy, A.; Ramamurthy, V. Acc. Chem. Res. 2003, 36, 509. (3) (a) Nakamura, A.; Inoue, Y. J. Am. Chem. Soc. 2003, 125, 966. (b) Nakamura, A.; Inoue, Y. J. Am. Chem. Soc. 2005, 127, 5338. (c) Yang, C.; Mori, T.; Origane, Y.; Ko, Y. H.; Selvapalam, N.; Kim, K.; Inoue, Y. J. Am. Chem. Soc. 2008, 130, 8574. (d) Ke, C.; Yang, C.; Mori, T.; Wada, T.; Liu, Y.; Inoue, Y. Angew. Chem., Int. Ed. 2009, 48, 6675. (e) Yang, C.; Ke, C.; Liang, W.; Fukuhara, G.; Mori, T.; Liu, Y.; Inoue, Y. J. Am. Chem. Soc. 2011, 133, 13786.

Table 1. Enantiodifferentiating Photocyclodimerization of 2-Anthracenecarboxylic Acid (AC) through Competitive 1:1 and 2:1 Complexation with Hydrogen-Bonding Template 4-Benzamidoprolinol (TKS159)a % AC-TKS complexb

% eec

product distribution/%

[TKS]0/[AC]0

1:1

2:1

irradiation time/min

% conversion

1

2

3

4

2

3

HH/HTd

0 0.25 0.5 1.0 1.6 2.4 4.0 10 40 120

0 11 20 35 48 60 73 88 97 99

0 0.24 0.40 0.56 0.61 0.58 0.48 0.25 0.07 0.02

3.0 3.5 3.0 3.0 2.8 2.8 3.0 3.0 5.0 6.0

9 12 11 12 10 8 10 6 11 12

33 31 30 29 28 28 28 32 35 40

23 20 20 19 17 17 20 20 25 28

24 26 28 29 29 28 27 28 26 24

20 23 22 23 26 27 25 20 14 8

0 2 8 14 20 21 25 30 30 28

0 1 3 6 4 5 10 8 18 24

0.79 0.96 1.00 1.08 1.22 1.22 1.08 0.92 0.67 0.47

[AC]0 = 0.25 mM; irradiated at >320 nm in CH2Cl2 at 25 °C. b Composition of 1:1 and 2:1 complexes calculated by using K1 = 3400 M1 and K2 = 100 M1; see Figure S8 and Table S3 in the Supporting Information. c Enantiomeric excess determined by chiral HPLC (error in ee e2%); the negative ee indicates the favored formation of the second-eluted enantiomer; for the absolute configurations of 2 and 3, see: Wakai, A.; Fukasawa, H.; Yang, C.; Mori, T.; Inoue, Y. J. Am. Chem. Soc. 2012, 134, 4990 and 10306. d HH/HT = ([3] þ [4])/([1] þ [2]). a

environment in the ground state and then to control the stereochemical fate of confined substrate(s) in the excited state. The chiral H-bonding template is a simpler, yet effective, tool for manipulating the stereochemical outcomes of photochirogenic reactions.57 In this strategy, the chiral template shields one of the enantiotopic faces of a prochiral substrate to block the intra- or intermolecular attack of a built-in or external reagent, facilitating the attack from the open face to give chiral photoproduct(s) often in goodhigh optical yields.5,7 In our recent work on enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid (AC) mediated by 4-amino-5-chloro-2-methoxy-N-((2S,4S)-(1ethyl-2-hydroxymethyl-4-pyrrolidinyl))benzamide (TKS159) (Scheme 1),7 we have shown that TKS forms a 1:1 complex with AC through a unique hydrogen-bonding motif incorporating the TKS’s prolinol and the AC’s carboxyl. In the photocyclodimerization experiments, we used high TKS/AC ratios of 3 to 120 in order to secure the >99% complexation and obtained cyclodimers 2 and 3 in comparable enantiomeric excesses (ee) of 40% upon irradiation at >320 nm in dichloromethane at 50 °C.7b Further photophysical studies revealed the existence of diastereomeric re- and si-[AC•TKS] precursor complexes, which differ in fluorescence maximum and lifetime.7b

Scheme 1. Complexation and Photocyclodimerization of AC with Chiral Hydrogen-Bonding Template TKS159

Org. Lett., Vol. 14, No. 18, 2012

In our effort to elucidate the detailed complexation and photochirogenic behaviors of AC with TKS, we examined the effects of AC:TKS stoichiometry on product ratio and ee, which led us to the unexpected results shown in Table 1 (where the conversion was kept low (e12%) to avoid any significant deviation from the initial stoichiometry). As anticipated, the absolute ee of 2 smoothly increased with increasing concentration of TKS, more exactly the concentration of the [AC•TKS] complex or % AC complexed. However, the ee of 3 stayed low (