Citation: Yuefei Gu, Tianyang Wang, Ming Gao, Zhu-Jun Yao. Scalable Cu(Ⅱ)-mediated intramolecular dehydrogenative phenol-phenol coupling: Concise synthesis of enantiopure axially chiral homo- and hetero-diphenols[J]. Chinese Chemical Letters, ;2021, 32(1): 380-384. doi: 10.1016/j.cclet.2020.02.015 shu

Scalable Cu(Ⅱ)-mediated intramolecular dehydrogenative phenol-phenol coupling: Concise synthesis of enantiopure axially chiral homo- and hetero-diphenols

State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

gaom@nju.edu.cn

yaoz@nju.edu.cn

Received Date: 15 January 2020
Revised Date: 21 January 2020
Accepted Date: 10 February 2020
Available Online: 11 February 2020

Figures(4)

An intramolecular dehydrogenative homo- and hetero-coupling of phenols has been successfully developed for quick preparation of enantiopure axial diphenols under mild Cu(Ⅱ)-mediated conditions, using ((4S, 5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)dimethanol as the chiral auxiliary. The commercially available (R)-α-methylbenzylamine was identified as the best amine ligand for Cu(Ⅱ) in the reactions. A variety of homo/hetero bis-dihydroxylbenzoate substrates were examined, affording the corresponding axially chiral diphenols with satisfactory to excellent diastereomeric ratios, and a representative scalable preparation was also attempted. A formal synthesis of natural product (+)-deoxyschizandrin has been achieved in this work using one axially chiral diphenol as the synthetic intermediate.
- Axially chirality,
- Dehydrogenative phenol-phenol coupling,
- Cu(Ⅱ)-mediated oxidation,
- Chiral auxiliary,
- Diastereoselectivity
1. [1]
  (a) G. Bringmann, A.J.P. Mortimer, P.A. Keller, et al., Angew. Chem. Int. Ed. 44 (2005) 5384-5427;
  (b) G. Bringmann, M.C. Günther, O. Schupp, S. Taster, Biaryls innature: a multifacettedclass of stereochemically, biosynthetically, and pharmacologically intriguing secondary metabolites, in: W. Herz, H. Falk, G.W. Kirby, R.E. Moore (Eds.), Progress in the Chemistry of Organic Natural Products, 82, Springer, New York, 2001, pp. 1-293;
  (c) G. Bringmann, T. Gulder, T.A.M. Gulder, M. Breuning, Chem. Rev. 111 (2011) 563-639;
  (d) F. Lv, Z.J. Yao, Sci. China Chem. 60 (2017) 701-720.
2. [2]
  (a) T. Qin, S.L. Skraba-Joiner, Z.G. Khalil, et al., Nat. Chem. 7 (2015) 234-240;
  (b) B.B. Liau, B.C. Milgram, M.D. Shair, J. Am. Chem. Soc. 134 (2012) 16765-16772.
3. [3]
  (a) J.M. Gao, S.X. Yang, J.C. Qin, Chem. Rev. 113 (2013) 4755-4811;
  (b) M.C. Kozlowski, B.J. Morgan, E.C. Linton, Chem. Soc. Rev. 38 (2009) 3193-3207.
4. [4]
  H. Kang, C. Torruellas, J. Liu, M.C. Kozlowski, Org. Lett. 20 (2018) 5554-5558. doi: 10.1021/acs.orglett.8b02183
5. [5]
  W.W. Chen, Q. Zhao, M.H. Xu, G.Q. Lin, Org. Lett. 12 (2010) 1072-1075. doi: 10.1021/ol1000632
6. [6]
  (a) T. Biftu, B.G. Hazra, R. Stevenson, J. Chem. Soc. Perkin Trans. I 1 (1979) 2276-2281;
  (b) T. Takeya, T. Okubo, S. Nishida, S. Tobinaga, Chem. Pharm. Bull. 33 (1985) 3599-3607.
7. [7]
  B.H. Lipshutz, F. Kayser, Z.P. Liu, Angew. Chem. Int. Ed. 33 (1994) 1842-1844. doi: 10.1002/anie.199418421
8. [8]
  B. Feringa, H. Wynberg, Bioorg. Chem. 7 (1978) 397-408. doi: 10.1016/0045-2068(78)90031-7
9. [9]
  (a) J. Brussee, J.L.G. Groenendijk, J.M. teKoppele, A.C.A. Jansen, Tetrahedron 41 (1985) 3313-3319;
  (b) M. Smrčina, M. Lorenc, V. Hanuš, P. Sedmera, P. Kočovský, J. Org. Chem. 579 (1992) 1917-1920;
  (c) Z. Xu, M.C. Kozlowski, J. Org. Chem. 67 (2002) 3072-3078;
  (d) X.L. Li, J. Yang, M.C. Kozlowski, Org. Lett. 3 (2001) 1137-1140;
  (e) P. Miko, J. Roithová, D. Schröder, J. Lemaire, H. Schwarz, M.C. Holthausen, Chem. Eur. J. 14 (2008) 4318-4327;
  (f) M. Nakajima, I. Miyashi, K. Kanayama, S. Hashimoto, J. Org. Chem. 64 (1999) 2264-2271.
10. [10]
  (a) N. Asakura, S. Fujimoto, N. Michihata, et al., J. Org. Chem. 76 (2011) 9711-9719;
  (b) T. Hirokane, Y. Hirata, T. Ishimoto, K. Nishii, H. Yamada, Nat. Commun. 5 (2014) 3478.
11. [11]
  (a) B.H. Lipshutz, B. James, S. Vance, I. Carrico, Tetrahedron Lett. 38 (1997) 753-756;
  (b) B.H. Lipshutz, Y.J. Shin, Tetrahedron Lett. 39 (1998) 7010-7020.
12. [12]
  (a) Y. Kasai, N. Michihata, H. Nishimura, T. Hirokane, H. Yamada, Angew. Chem. Int. Ed. 51 (2012) 8026-8029;
  (b) N. Michihata, Y. Kaneko, Y. Kasai, et al., J. Org. Chem. 78 (2013) 4319-4328;
  (c) H. Takeuchi, K. Mishiro, Y. Ueda, et al., Angew. Chem. Int. Ed. 54 (2015) 6177-6180;
  (d) B. Fering, H. Wynberg, Bioorg. Chem. 7 (1978) 397-408.
13. [13]
  A.S. Hay, H.S. Blanchard, G.F. Endres, J.W. Eustance, J. Am. Chem. Soc. 81 (1959) 6335-6336. doi: 10.1021/ja01532a062
14. [14]
  (a) G. Bott, L.D. Field, S. Sternhell, J. Am. Chem. Soc. 102 (1980) 5618-5626;
  (b) M. Rieger, F.H. Westheimer, J. Am. Chem. Soc. 72 (1950) 19-28.
15. [15]
  A.I. Meyers, T.D. Nelson, H. Moorlag, D.J. Rawson, A. Meier, Tetrahedron 60 (2004) 4459-4473. doi: 10.1016/j.tet.2004.01.095
16. [16]
  A.R. Carroll, R.W. Read, W.C. Taylor, Aust. J. Chem. 47 (1994) 1579-1589. doi: 10.1071/CH9941579
1. [1]
  Qian CHENG , Takayuki ORITANI , Alfred HASSNER . High Diastereoselectivity in the Conjugate Addition of Functionalized Alcohols to a Chiral(E)-Nitroalkene. Chinese Chemical Letters, 1999, 10(8): 629-632.
2. [2]
  P. B. Thorat , S. V. Goswami , V. P. Sondankar , S. R. Bhusare . Stereoselective synthesis of vic-halohydrins and an unusual Knoevenagel product from an organocatalyzed aldol reaction: A non-enamine mode. Chinese Journal of Catalysis, 2015, 36(7): 1093-1100. doi: 10.1016/S1872-2067(14)60317-X
3. [3]
  Xiu Min SHEN , Liang Dong SUN , Cong ZHANG . Studies on Diastereoselective Intramolecular meta-Cycloaddition of Arene to Olefin (Part Ⅱ). Chinese Chemical Letters, 1998, 9(4): 321-323.
4. [4]
  Xiu Min SHEN , Xiao Chuan GUO , Liang Dong SUN , Cong ZHANG . Studies on Diastereoselective Intramolecular meta-Cycloaddition ofArene to Olefin (Part I). Chinese Chemical Letters, 1998, 9(2): 131-134.
5. [5]
  Zhi Hua MA , Cong LIU , Yong Hua ZHAO , Wei LI , Jian Bo WANG . Diastereoselective α-Alkylation of β-Amino Esters:Preparation of Novel α-Substituted β-Amino Esters from α-Amino Acids. Chinese Chemical Letters, 2002, 13(8): 721-724.
6. [6]
  Wu Zhen , Feng Xue-Xin , Wang Qing-Dong , Liu Xuan-Yu , Rao Weidong , Yang Jin-Ming , Shen Zhi-Liang . An efficient Bi/NH₄I-mediated addition reaction for the highly diastereoselective synthesis of homoallylic alcohols in aqueous media. Chinese Chemical Letters, 2020, 31(2): 391-395. doi: 10.1016/j.cclet.2019.07.030
7. [7]
  Wang Yang , Lan Yu . Mechanism and origin of diastereoselectivity of N-heterocyclic carbene-catalyzed cross-benzoin reaction: A DFT study. Chinese Chemical Letters, 2020, 31(3): 736-738. doi: 10.1016/j.cclet.2019.08.010
8. [8]
  Zou Xuejie , Liu Yangzi , Shang Shaojing , Yang Wulin , Deng Weiping . Diastereoselective synthesis of functionalized tetrahydro-γ-carbolines via a [3 + 3] cycloaddition of 2, 2'-diester aziridines with β-(indol-2-yl)-α, β-unsaturated ketones. Chinese Chemical Letters, 2020, 31(5): 1293-1296. doi: 10.1016/j.cclet.2019.09.002
9. [9]
  Jinshan Li , Wenxue Xi , Saimei Liu , Yaqi Yang , Jianguo Yang , Hanfeng Ding , Zhiming Wang . HFIP-catalyzed highly diastereoselective formal [4 + 2] cyclization to synthesize difluorinated multisubstituted chromans using difluoroenoxysilanes as C2 synthons. Chinese Chemical Letters, 2022, 33(6): 3007-3011. doi: 10.1016/j.cclet.2021.12.002
10. [10]
  Meng-Fan Li , Shao-Qing Shi , Ting Xu , Qian Zhang , Wen-Juan Hao , Shu-Liang Wang , Jianyi Wang , Shu-Jiang Tu , Bo Jiang . Stereoselective construction of azepine-containing bridged scaffolds via organocata-lytic bicyclization of yne-allenone esters with nitrones. Chinese Chemical Letters, 2023, 34(4): 107751-1-107751-4. doi: 10.1016/j.cclet.2022.107751
11. [11]
  Xiao An Zhang . DIASTEREOSELECTIVITY OF ALLYBORATION OF ALDEHYDES. Chinese Chemical Letters, 1991, 2(2): 133-134.
12. [12]
  CHAI Zhuo . Descriptors for Stereoselectivity of Organic Reactions: %ee,%de or er, dr?. University Chemistry, 2017, 32(3): 60-62. doi: 10.3866/PKU.DXHX201608016
13. [13]
  Zhang Suihong , Xie Zongbo , Yang Xiaoli , Le Zhanggao . Synthesis of Tetrahydrothiophene Derivatives by Enzymatic Cascade Michael-Aldol Reaction. Chemistry, 2016, 79(8): 768-770.
14. [14]
  Alekha Kumar Sutar , Yasobanta Das , Sasmita Pattnaik , Anita Routaray , Nibedita Nath , Prasanta Rath , Tungabidya Maharana . Novel polystyrene-anchored zinc complex：Efficient catalyst for phenol oxidation. Chinese Journal of Catalysis, 2014, 35(10): 1701-1708. doi: 10.1016/S1872-2067(14)60113-3
15. [15]
  Deyin Wang , Hongkai Liu , Wei Wang . Chirality and chiral functional composites of bicontinuous cubic nanostructured cubosomes. Chinese Chemical Letters, 2022, 33(3): 1488-1492. doi: 10.1016/j.cclet.2021.08.040
16. [16]
  Dong-Dong Zhang , Yun-Long Liu , Yan Wang , Hao Wei , Min Shi , Fei-Jun Wang . Synthesis of axially chiral oxazoline-carbene coordinated palladium complexes with a N-phenyl framework. Chinese Chemical Letters, 2016, 27(4): 563-565.
17. [17]
  Xing Yue WEI , Sheng Ying QIN . Dioxygen Affinities and Catalytic Oxidation Performance of Co (Ⅱ) Complexes with Phenol Ether Bridged Dihydroxamic Acids. Chinese Chemical Letters, 2006, 17(9): 1259-1262.
18. [18]
  Longjiang Sun , Dongxu Wang , Yuxin Li , Baogang Wu , Qi Li , Cheng Wang , Shuao Wang , Baojiang Jiang . Fully conversing and highly selective oxidation of benzene to phenol based on MOFs-derived CuO@CN photocatalyst. Chinese Chemical Letters, 2023, 34(4): 107490-1-107490-4. doi: 10.1016/j.cclet.2022.05.004
19. [19]
  Long-Duo Zhang , Cui-Fen Lu , Zu-Xing Chen , Gui-Chun Yang , Jun-Qi Nie . Diastereoselective alkylation reactions employing a new camphor-based 2-phenylimino-2-oxazolidine chiral auxiliary. Chinese Chemical Letters, 2014, 25(11): 1466-1468. doi: 10.1016/j.cclet.2014.05.044
20. [20]
  Shi Xiaodong , Jiang Yixiang , Yang Dan , Zhao Hui , Tian Yuan , Li Zigang . Reversibly switching the conformation of short peptide through in-tether chiral sulfonium auxiliary. Chinese Chemical Letters, 2018, 29(3): 485-488. doi: 10.1016/j.cclet.2017.07.003

Get Citation

PDF

XML

Metrics

PDF Downloads(20)
Abstract views(995)
HTML views(143)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142