Synthesis, Table of Contents Synthesis 2019; 51(02): 557-563DOI: 10.1055/s-0037-1610831 paper © Georg Thieme Verlag Stuttgart · New York Synthesis and Optical Resolution of 3,3,3′,3′-Tetramethyl-1,1′-spirobiindane-7,7′-diol Qiaoxia Zhou , Rihuang Pan , Huanyu Shan , Xufeng Lin * Laboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China Email: lxfok@zju.edu.cn › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract A novel chiral C2-symmetric spiro diol, 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol (TMSIOL), was conveniently prepared via practical seven-step route from Bisphenol A in 45.1% overall yield. l-Menthyl chloroformate is used as optical resolving agent for the separation of the two enantiomers of TMSIOL. Key words Key wordsasymmetric catalysis - chiral ligand - chiral diol - spirobiindane - resolution Full Text References References 1a Ojima I. Catalytic Asymmetric Synthesis . Wiley-VCH; Weinheim: 2000 1b Jacobsen EN. Pfaltz A. Yamamoto H. Comprehensive Asymmetric Catalysis . Vol. 1–3. Springer; Berlin: 1999 1c Brunel JM. Chem. Rev. 2005; 105: 857 1d McCarthy M. Guiry PJ. Tetrahedron 2001; 57: 3809 1e Whitesell JK. Chem. Rev. 1989; 89: 1581 2a Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal. 2006; 348: 999 2b Akiyama T. Chem. Rev. 2007; 107: 5744 2c Terada M. Chem. Commun. 2008; 44: 4097 2d Adair G. Mukherjee S. List B. Aldrichimica Acta 2009; 41: 31 2e Yu J. Shi F. Gong L.-Z. Acc. Chem. Res. 2011; 44: 1156 2f Parmar D. Sugiono E. Raja S. Rueping M. Chem. Rev. 2014; 114: 9047 3a Brunel JM. Chem. Rev. 2007; 107: PR1 3b Chen Y. Yekta S. Yudin AK. Chem. Rev. 2003; 103: 3155 3c Brunel JM. Chem. Rev. 2005; 105: 857 3d Noyori R. Takaya H. Acc. Chem. Res. 1990; 23: 345 3e Berthod M. Mignani G. Woodward G. Lemaire M. Chem. Rev. 2005; 105: 1801 3f Rueping M. Kuenkel A. Atodiresei I. Chem. Soc. Rev. 2011; 40: 4539 4 Cramer N. Laschat S. Baro A. Organometallics 2006; 25: 2284 5a Hua Z. Vassar VC. Ojima I. Org. Lett. 2003; 5: 3831 5b Shi C. Chien CW. Ojima I. Chem. Asian J. 2011; 6: 674 6a Seebach D. Beck AK. Heckel A. Angew. Chem. Int. Ed. 2001; 40: 92 6b Seebach D. Pichota A. Beck AK. Pinkerton AB. Litz T. Karjalainen J. Gramlich V. Org. Lett. 1999; 1: 55 7a Wulff W. Desai A. Synthesis 2010; 3670 7b Bao J. Wulff WD. Rheingold AL. J. Am. Chem. Soc. 1993; 115: 3814 8a Cram DJ. Steinberg H. J. Am.Chem. Soc. 1954; 76: 2753 8b Hardeggar E. Maeder E. Semarne HM. Cram DJ. J. Am. Chem. Soc. 1959; 81: 2729 8c Chan AS. C. Hu W. Pai C.-C. Lau C.-P. J. Am. Chem. Soc. 1997; 119: 9570 8d Srivastava N. Mital A. Kumar A. J. Chem. Soc., Chem. Commun. 1992; 493 9a Birman VB. Rheingold AL. Lam K.-C. Tetrahedron: Asymmetry 1999; 10: 125 9b Li Z. Liang X. Wu F. Wan B. Tetrahedron: Asymmetry 2004; 15: 665 10 Cheng X. Hou G.-H. Xie J.-H. Zhou Q.-L. Org. Lett. 2004; 6: 2381 11a Wu S. Zhang W. Zhang Z. Zhang X. Org. Lett. 2004; 6: 3565 11b Zhang W. Wang C.-J. Gao W. Zhang X. Tetrahedron Lett. 2005; 46: 6087 11c Zhang W. Wu S. Zhang Z. Yennawar H. Zhang X. Org. Biomol. Chem. 2006; 4: 4474 12a Xie J.-H. Zhou Q.-L. Acc. Chem. Res. 2008; 41: 581 12b Bajracharya GB. Arai MA. Koranne PS. Suzuki T. Takizawa S. Sasai H. Bull. Chem. Soc. Jpn. 2009; 82: 285 12c Ding K. Han Z. Wang Z. Chem. Asian J. 2009; 4: 32 12d Xie J.-H. Zhou Q.-L. Acta Chim. Sinica 2014; 72: 778 12e Liu Y. Li W. Zhang J. Natl. Sci. Rev. 2017; 4: 326 13a Chan AS. C. Hu WH. Pai CC. Lau CP. J. Am. Chem. Soc. 1997; 119: 9570 13b Arai MA. Kuraishi M. Arai T. Sasai H. J. Am. Chem. Soc. 2001; 123: 2907 13c Fu Y. Xie J.-H. Hu AG. Zhou H. Wang LX. Zhou Q.-L. Chem. Commun. 2002; 480 13d Zoraida F. Beentjes MS. Batema GD. Dieleman CB. van Strijdonck GP. F. Joost NH. R. Paul CJ. K. Jan F. Kees G. van Leeuwen PW. N. M. Angew. Chem. Int. Ed. 2003; 42: 1284 13e Xie J-H. Duan H-F. Fan B-M. Cheng X. Wang L-X. Zhou Q-L. Adv. Synth. Catal. 2004; 346: 625 13f Han ZB. Wang Z. Zhang XM. Ding KL. Angew. Chem. Int. Ed. 2009; 48: 5345 13g Li J. Chen G. Wang Z. Zhang R. Zhang XM. Ding K. Chem. Sci. 2011; 2: 1141 13h Wang XM. Meng FY. Wang Y. Han ZB. Chen YJ. Liu L. Wang Z. Ding KL. Angew. Chem. Int. Ed. 2012; 51: 9276 For recent examples from our group, see: 14a Xu F. Huang D. Han C. Shen W. Lin X. Wang Y. J. Org. Chem. 2010; 75: 8677 14b Huang D. Xu F. Lin X. Wang YG. Chem. Eur. J. 2012; 18: 3148 14c Li X. Zhao Y. Qu H. Mao Z. Lin X. Chem. Commun. 2013; 49: 1401 14d Huang D. Li X. Xu F. Li L. Lin X. ACS Catal. 2013; 3: 2244 14e Li X. Chen D. Gu H. Lin X. Chem. Commun. 2014; 50: 7538 14f Shen X. Wang Y. Wu T. Mao Z. Lin X. Chem. Eur. J. 2015; 21: 9039 14g Lou H. Wang Y. Jin E. Lin X. J. Org. Chem. 2016; 81: 2019 14h Xie E. Rahman A. Lin X. Org. Chem. Front. 2017; 4: 1407 For selected examples by other groups, see: 14i Čorić I. Müller S. List B. J. Am. Chem. Soc. 2010; 132: 17370 14j Xing C. Liao Y. Ng J. Hu Q. J. Org. Chem. 2011; 76: 4125 14k Xu B. Zhu S.-F. Xie X.-L. Shen J.-J. Zhou Q.-L. Angew. Chem. Int. Ed. 2011; 50: 11483 14l Rubush DM. Morges MA. Rose BJ. Thamm DH. Rovis T. J. Am. Chem. Soc. 2012; 134: 13554 14m Chen Z. Wang B. Wang Z. Zhu G. Sun J. Angew. Chem. Int. Ed. 2013; 52: 2027 14n Wu J. Wang Y. Drljevic A. Rauniyar V. Phipps R. Toste FD. Proc. Natl. Acad. Sci. U S A 2013; 110: 13729 14o Wang S.-G. You S.-L. Angew. Chem. Int. Ed. 2014; 53: 2194 14p Zhang Y. Zhao J. Jiang F. Sun S. Shi F. Angew. Chem. Int. Ed. 2014; 53: 13912 14q Gobé V. Guinchard X. Chem. Eur. J. 2015; 21: 8511 14r Rong Z. Zhang Y. Chua RH. B. Pan H. Zhao Y. J. Am. Chem. Soc. 2015; 137: 4944 14s Li S. Zhang J. Li X. Cheng D. Tan B. J. Am. Chem. Soc. 2016; 138: 16561 For a recent review focusing on SPAs, see: 14t Rahman A. Lin X. Org. Biomol. Chem. 2018; 16: 4753 15a Sun W. Gu H. Lin X. J. Org. Chem. 2018; 83: 4034 15b Chang S. Wang L. Lin X. Org. Biomol. Chem. 2018; 16: 2239 16a Fisher CH. Furlong RW. Grant M. J. Am. Chem. Soc. 1936; 58: 820 16b Molteni V. Rhodes D. Rubins K. Hansen M. Bushman FD. Siegel JS. J. Med. Chem. 2000; 43: 2031 16c Chen W.-F. Lin H.-Y. Dai SA. Org. Lett. 2004; 6: 2341 17 CCDC 1843734 contains the supplementary crystallographic data for compound 6a reported in this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. 18 CCDC 1845549 contains the supplementary crystallographic data for (R)-TMSIOL reported in this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. 19 CCDC 1854445 contains the supplementary crystallographic data for (S)-SPINOL reported in this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures. For reviews, see: 20a Marques CS. Burke AJ. ChemCatChem 2011; 3: 635 20b Tian P. Dong H.-Q. Lin G.-Q. ACS Catal. 2012; 2: 95 20c Chen D. Xu M.-H. Chin. J. Org. Chem. 2017; 37: 1589 For selected examples, see: 20d Duan H.-F. Jia Y.-X. Wang L.-X. Zhou Q.-L. Org. Lett. 2006; 8: 2567 20e Wang Z.-Q. Feng C.-G. Xu M.-H. Lin G.-Q. J. Am. Chem. Soc. 2007; 129: 5336 Supplementary Material Supplementary Material Supporting Information