Zn(salen)-Catalyzed Enantioselective Phenyl Transfer to Aldehydes and Ketones with Organozinc Reagent

Keisuke Shimizu; Hidenori Uetsu; Takashi Gotanda; Katsuji Ito

doi:10.1055/s-0034-1380461

Synlett, Table of Contents

Synlett 2015; 26(09): 1238-1242
DOI: 10.1055/s-0034-1380461

letter

Zn(salen)-Catalyzed Enantioselective Phenyl Transfer to Aldehydes and Ketones with Organozinc Reagent

Keisuke Shimizu

Department of Chemistry, Fukuoka University of Education, Akama, Munakata, Fukuoka, 811-4192, Japan Email: itokat@fukuoka-edu.ac.jp

,

Hidenori Uetsu

Department of Chemistry, Fukuoka University of Education, Akama, Munakata, Fukuoka, 811-4192, Japan Email: itokat@fukuoka-edu.ac.jp

,

Takashi Gotanda

Department of Chemistry, Fukuoka University of Education, Akama, Munakata, Fukuoka, 811-4192, Japan Email: itokat@fukuoka-edu.ac.jp

,

Katsuji Ito*

Department of Chemistry, Fukuoka University of Education, Akama, Munakata, Fukuoka, 811-4192, Japan Email: itokat@fukuoka-edu.ac.jp

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Abstract

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Abstract

A chiral zinc complex of salen was found to be an efficient catalyst for the phenyl transfer of organozinc reagent to aromatic aldehydes and ketones. High enantioselectivities were obtained in reactions of both aromatic aldehydes and ketones (up to 97% and 92% ee, respectively).

Key words

Zn(salen) complex - asymmetric catalysis - phenyl transfer - aldehydes - ketones - diarylmethanol

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References

References and Notes

1a Harms AF, Nauta WT. J. Med. Pharm. Chem. 1960; 2: 57
1b Meguro K, Aizawa M, Sohda T, Kawamatsu Y, Nagaoka A. Chem. Pharm. Bull. 1985; 33: 3787
1c Toda F, Tanaka K, Koshiro K. Tetrahedron: Asymmetry 1991; 2: 873
1d Stanev S, Rakovska R, Berova N, Snatzke G. Tetrahedron: Asymmetry 1995; 6: 183
1e Botta M, Summa V, Corelli F, Di Pietro G, Lombardi P. Tetrahedron: Asymmetry 1996; 7: 1263

2a Bolm C, Hermanns N, Hildebrand JP, Muñiz K. Angew. Chem. Int. Ed. 2000; 39: 3465
2b Bolm C, Kesselgruber M, Hermanns N, Hilderbrand JP. Angew. Chem. Int. Ed. 2001; 40: 1488
2c Bolm C, Rudolph J. J. Am. Chem. Soc. 2002; 124: 14850
2d Rudolph J, Hermanns N, Bolm C. J. Org. Chem. 2004; 69: 3997

For selected reviews, see:

3a Binder CM, Singaram B. Org. Prep. Proced. Int. 2011; 43: 139
3b Paixão MW, Braga AL, Lüdtke DS. J. Braz. Chem. Soc. 2008; 19: 813
3c Schmidt F, Stemmler RT, Rudolph J, Bolm C. Chem. Soc. Rev. 2006; 35: 454
3d Bolm C, Hildebrand JP, Muniz K, Hermanns N. Angew. Chem. Int. Ed. 2001; 40: 3284
3e Pu L, Yu H.-B. Chem. Rev. 2001; 101: 757

For recent selected examples of aryl transfer to aldehydes using arylzinc reagent, see:

4a Song X, Hua Y.-Z, Shi J.-G, Sun P.-P, Wang M.-C, Chang J. J. Org. Chem. 2014; 79: 6087
4b Jia X, Lin A, Mao Z, Zhu C, Cheng Y. Molecules 2011; 16: 2971
4c Hatano M, Mizuno T, Ishihara K. Tetrahedron 2011; 67: 4417
4d Hatano M, Gouzu R, Mizuno T, Abe H, Yamada T, Ishihara K. Catal. Sci. Technol. 2011; 1: 1149
4e Godoi M, Alberto EE, Paixão MW, Soares LA, Schneider PH, Braga AL. Tetrahedron 2010; 66: 1341
4f Salvi L, Kim JG, Walsh PJ. J. Am. Chem. Soc. 2009; 131: 12483
4g Yang X.-F, Hirose T, Zhang G.-Y. Tetrahedron: Asymmetry 2009; 20: 415
4h Huang X, Wu L, Xu J, Zong L, Hu H, Cheng Y. Tetrahedron Lett. 2008; 46: 6823
4i Rodríguez-Escrich S, Reddy KS, Jimeno C, Colet G, Rodríguez-Escrich C, Solà L, Vidal-Ferran A, Pericàs MA. J. Org. Chem. 2008; 73: 5340
4j Wang M.-C, Wang X.-D, Ding X, Liu Z.-K. Tetrahedron 2008; 64: 2559
4k Jin M.-J, Sarkar SM, Lee D.-H, Qiu H. Org. Lett. 2008; 10: 1235
4l Wang M.-C, Zhang Q.-J, Zhao W.-X, Wang X.-D, Ding X, Jing T.-T, Song M.-P. J. Org. Chem. 2008; 73: 168
4m Sedelmeier J, Bolm C. J. Org. Chem. 2007; 72: 8859
4n Zhong J, Guo H, Wang M, Yin M, Wang M. Tetrahedron: Asymmetry 2007; 18: 734
4o Schmidt F, Rudolph J, Bolm C. Adv. Synth. Catal. 2007; 349: 703
4p Paixão MW, de Godoi M, Rhoden CR. B, Westermann B, Wessjohann LA, Lüdtke DS, Braga AL. J. Mol. Catal. A: Chem. 2007; 261: 120
4q Ahern T, Müller-Bunz H, Guiry PJ. J. Org. Chem. 2006; 71: 7596
4r Hatano M, Miyamoto T, Ishihara K. J. Org. Chem. 2006; 71: 6474
4s Lu G, Kwong FY, Ruan J.-W, Li Y.-M, Chan AS. C. Chem. Eur. J. 2006; 12: 4115
4t Wang M.-C, Zhao W.-X, Wang X.-D, Song M.-P. Synlett 2006; 3443
4u Braga AL, Milani P, Vargas F, Paixão MW, Sehnem JA. Tetrahedron: Asymmetry 2006; 17: 2793
4v Chai Z, Liu X.-Y, Wu X.-Y, Zhao G. Tetrahedron: Asymmetry 2006; 17: 2442
4w Wu P.-Y, Wu H.-L, Uang B.-J. J. Org. Chem. 2006; 71: 833
4x Qin Y.-C, Pu L. Angew. Chem. Int. Ed. 2006; 45: 273
4y Ito K, Tomita Y, Katsuki T. Tetrahedron Lett. 2005; 46: 6083

For reviews on selective addition of organometal reagent to carbonyl compounds, see:

5a Hatano M, Miyamoto T, Ishihara K. Curr. Org. Chem. 2007; 11: 127
5b Hatano M, Ishihara K. Synthesis 2008; 1647

6 Dosa PI, Fu GC. J. Am. Chem. Soc. 1998; 120: 445

7a Betancort JM, García C, Walsh PJ. Synlett 2004; 749
7b Li H, García C, Walsh PJ. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 5425
7c García C, Walsh PJ. Org. Lett. 2003; 5: 3641

8a Forrat VJ, Ramón DJ, Yus M. Tetrahedron: Asymmetry 2009; 20: 65
8b Forrat VJ, Ramón DJ, Yus M. Tetrahedron: Asymmetry 2008; 19: 537
8c Forrat VJ, Prieto O, Ramón DJ, Yus M. Chem. Eur. J. 2006; 12: 4431
8d Forrat VJ, Prieto O, Ramón DJ, Yus M. Chem. Eur. J. 2006; 12: 6727
8e Prieto O, Ramón DJ, Yus M. Tetrahedron: Asymmetry 2003; 14: 1955

9a Hatano M, Ishihara K. Chem. Rec. 2008; 8: 143
9b Hatano M, Miyamoto T, Ishihara K. Org. Lett. 2007; 9: 4535

For selected examples of other methods of synthesis of chiral diarylmethanols from aldehydes or ketones, see:

10a Yang Y.-X, Liu Y, Zhang L, Jia Y.-E, Wang P, Zhuo F.-F, An X.-T, Da C.-S. J. Org. Chem. 2014; 79: 10696
10b Li K, Hu N, Luo R, Yuan W, Tang W. J. Org. Chem. 2013; 78: 6350
10c Sui Y.-Z, Zhang X.-C, Wu J.-W, Li S, Zhou J.-N, Li M, Fang W, Chan AS. C, Wu J. Chem. Eur. J. 2012; 18: 7486
10d Glynn D, Shannon J, Woodward S. Chem. Eur. J. 2010; 16: 1053
10e Zou S, Wu K.-H, Chen C.-A, Gau H.-M. J. Org. Chem. 2009; 74: 3500
10f Chen C.-A, Wu K.-H, Gau H.-M. Adv. Synth. Catal. 2008; 350: 1626
10g Chen C.-A, Wu K.-H, Gau H.-M. Angew. Chem. Int. Ed. 2007; 46: 5373
10h Tomita D, Wada R, Kanai M, Shibasaki M. J. Am. Chem. Soc. 2005; 127: 4138

11a Cozzi PG, Papa A, Umani-Ronchi A. Tetrahedron Lett. 1996; 37: 4613
11b Alesi S, Emer E, Capdevila MG, Petruzziello D, Gualandi A, Cozzi PG. Molecules 2011; 16: 5298
11c Cozzi PG. Angew. Chem. Int. Ed. 2003; 42: 2895
11d Pathak K, Bhatt AP, Abdi SH. R, Kureshy RI, Khan N.-UH, Ahmad I, Jasra RV. Chirality 2007; 19: 82

12a DiMauro EF, Kozlowski MC. J. Am. Chem. Soc. 2002; 124: 12668
12b DiMauro EF, Kozlowski MC. Org. Lett. 2001; 3: 3053

13 Saito B, Katsuki T. Synlett 2004; 1557
14 Although the structure of the actual zinc species is still unclear, it is believed that the formation of PhZnEt is occurred, based on the theoretical studies. For recent study, see: Rudolph J, Bolm C, Norrby P.-O. J. Am. Chem. Soc. 2005; 127: 1548 ; and references cited therein

For enantioselective conversion of secondary alcohols into tertiary alcohols, see:

15a Bagutski V, French RM, Aggarwal VK. Angew. Chem. Int. Ed. 2010; 49: 5142
15b Stymiest JL, Bagutski V, French RM, Aggarwal VK. Nature (London, U.K.) 2008; 456: 778

16 Cozzi presumed that the absolute configurations of the tertiary propargylic alcohols from the alkynyl transfer to ketones in the presence of (R, R)-Zn(salen) are S.^11c However, some of these alcohols seems to be R according to the recent study on the determination of the absolute configurations of the tertiary propargylic alcohols.¹⁷ Abdi et al. reported that the addition of phenylacetylene to arylmethylketones in the presence of (R,R)-Zn(salen) gave R alcohols through the si-face attack of ketones.^11d
17 Kotani S, Kukita K, Tanaka K, Ichibakase T, Nakajima M. J. Org. Chem. 2014; 79: 4817
18 At present, we do not have any evidence to explain the changeover of the stereoselectivity in the reactions of aliphatic ketones.
19 Typical Experimental Procedure is Exemplified by Enantioselective Phenyl Transfer to p-Chlorobenzaldehyde Diphenylzinc (43.9 mg, 0.2 mmol) was placed in a flask under nitrogen, and diethylzinc (0.38 mL, 1.06 mol·dm^–3 in hexane) was added at r.t. and stirred for 30 min at the temperature. This suspension was added to a solution of salen 1 (10.9 mg, 0.02 mmol) in toluene (0.25 mL) and further stirred at the temperature for 30 min. After the mixture was cooled to –40 °C, p-chlorobenzaldehyde (28.1 mg, 0.2 mmol) was added. After being stirred for 1 h at the same temperature, the mixture was quenched with sat. aq NH₄Cl, allowed to warm to r.t., and extracted with Et₂O and then washed with sat. aq NaCl. The organic extract was dried over anhydrous Na₂SO₄ and concentrated. Silica gel chromatography of the residue (hexane–EtOAc, 19:1 to 9:1) gave the desired product (41.4 mg, 95%) as an oil. The ee of the product was determined to be 94% by HPLC using chiral stationary-phase column as described in the footnote b of Table 1. [α]_D ¹³ +20.2 (c 0.45, CHCl₃) [lit.^10d [α]_D ²³ +19.1 (c 0.83, CHCl₃) for 83% ee, (S)]. All spectral data of products in Tables 1–3 were in accordance with those reported in the literature. Specific Rotation of some Compounds (R)-Cyclohexylphenylmethanol [α]_D ²⁶ +33.9 (c 0.2, CHCl₃) for 76% ee [lit.^10d [α]_D ²³ +38.0 (c 0.4, CHCl₃) for 96% ee, (R)]. (S)-1-(4-Chlorophenyl)-1-phenylethanol [α]_D ¹³ +13.2 (c 0.2, CHCl₃) for 92% ee [lit.^15b [α]_D ²² +14.8 (c 6.5, CHCl₃) for 98% ee, (S)]. (S)-Phenylindan-1-ol [α]_D ¹⁷ +36.9 (c 1.6, CHCl₃) for 88% ee [lit.^15b [α]_D ²⁴ –33.3 (c 1.05, CHCl₃) for 88% ee, (R)]. (S)-1-Cyclohexyl-1-phenylethanol [α]_D ¹³ –7.1 (c 0.75, CH₂Cl₂) for 44% ee [lit.^15a [α]_D ²⁴ +17.9 (c 3.4, CH₂Cl₂) for 99% ee, (R)].