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DOI: 10.1055/s-0037-1610652
Stereoretentive Suzuki–Miyaura and Kumada–Tamao–Corriu Cross-Couplings for Preparing (E)- and (Z)-Stereodefined, Fully Substituted α,β-Unsaturated Esters: Application for a Pharmacophore Synthesis
This research was partially supported by Grants-in-Aid for Scientific Research on Basic Areas (B) ‘18350056’, Priority Areas (A) ‘17035087’ and ‘18037068’, (C) ‘15K05508’, and Exploratory Research ‘17655045’ from the Ministry of Education, Culture, Sports, Science and Technology (MEXT).Publication History
Received: 05 June 2018
Accepted after revision: 12 July 2018
Publication Date:
23 August 2018 (online)
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Dedicated to Professor Teruaki Mukaiyama on the celebration of his 90th birthday (Sotuju)
Abstract
Substrate-general stereocomplementary Suzuki–Miyaura (SM) cross-coupling and relevant Kumada–Tamao–Corriu (KTC) cross-coupling reactions for preparing (E)- and (Z)-stereodefined, fully substituted α,β-unsaturated esters are described. The SM cross-coupling reactions were performed under Pd(OAc)2/SPhos/iPr2NEt catalysis (24 examples, 66–99% yield). The KTC cross-coupling reactions were also performed under similar Pd(OAc)2/SPhos conditions (11 examples, 50–98% yield). Application to a useful pharmacophore containing a cyclopropane structure was investigated, wherein distinctive (E)- and (Z)-stereochemical difference between XPhos and SPhos was observed. A plausible mechanism for the stereoretention and stereoinversion cross-coupling reactions is proposed.
Key words
Suzuki–Miyaura cross-coupling - Kumada–Tamao–Corriu cross-coupling - fully substituted α,β-unsaturated esters - pharmacophore - stereoretention - XPhos - SPhosSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610652.
- Supporting Information
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References
- 1a Flynn AB. Ogilvie WW. Chem. Rev. 2007; 107: 4698
- 1b Smith MB. March’s Advanced Organic Chemistry . Wiley; New York: 2007. 6th ed., Chap. 12
- 1c Kürti L. Czakó B. Strategic Applications of Named Reactions in Organic Synthesis. Elsevier; Burlington: 2005: 196
- 2a Baxter JM. Steinhuebel D. Palucki M. Davies IW. Org. Lett. 2005; 7: 215
- 2b Steinhuebel D. Baxter JM. Palucki M. Davies IW. J. Org. Chem. 2005; 70: 10124
- 2c Klapars A. Campos KR. Chen CY. Volante RP. Org. Lett. 2005; 7: 1185
- 2d Nakatsuji H. Ueno K. Misaki T. Tanabe Y. Org. Lett. 2008; 10: 2131
- 2e Nakatsuji H. Nishikado H. Ueno K. Tanabe Y. Org. Lett. 2009; 11: 4258
- 2f Ashida Y. Sato Y. Honda A. Nakatsuji H. Tanabe Y. Synthesis 2016; 48: 4072
- 2g Ashida Y. Sato Y. Honda A. Nakatsuji H. Tanabe Y. Synform 2017; A38
- 3 Nakatsuji H. Ashida Y. Hori H. Sato Y. Honda A. Taira M. Tanabe Y. Org. Biomol. Chem. 2015; 13: 8205
- 4 Rivera AC. P. Still R. Franz DE. Angew. Chem. Int. Ed. 2016; 55: 6689
- 5 Ashida Y. Sato Y. Suzuki T. Ueno K. Kai K. Nakatsuji H. Tanabe Y. Chem. Eur. J. 2015; 21: 5934
- 6 Ashida Y. Honda A. Sato Y. Nakatsuji H. Tanabe Y. ChemistryOpen 2017; 6: 73
- 7 Nishikado H. Nakatsuji H. Ueno K. Nagase R. Tanabe Y. Synlett 2010; 2087
- 8 Ashida Y. Nakatsuji H. Tanabe Y. Org. Synth. 2017; 94: 93
- 9 Christensen M. Nolting A. Shevlin M. Weisel M. Maligres PE. Lee J. Orr RK. Plummer CW. Tudge MT. Campeau L.-C. Ruck RT. J. Org. Chem. 2016; 81: 824
- 10 A 50 g-scale preparation was performed by Ti-Claisen self-condensation using methyl hexanoate with TiCl4 and Et3N at 0–5 °C for 1 h (93% yield); see ref. 3.
- 11 Tendency of (E/Z)-selectivities under the conditions [K2CO3/iPrOH–H2O (7:1), 60 °C, 2 h] was as follows: Pd(OAc)2/SPhos, 80:20; Pd(OAc)2/DavePhos, 70:30; Pd(dppe)Cl2, 62:38; Pd(PPh3)4, 60:40; Pd(PPh3)2Cl2, 53:47; Pd(OAc)2/XPhos, 47:53; Pd(dppf)Cl2, 46:54; Pd(dppb)Cl2, 39:61; Pd(OAc)2/PCy3, 24:76. The solvent effect on (E/Z)-selectivities using (E)-2a under the identical conditions was as follows: THF, 14:86; toluene, 18:82.
- 12 Negishi cross-coupling reactions are generally more reactive with regard to catalyst loading than SM cross-coupling reactions (ref. 6). Against this outcome in the previous report, the present SM cross-coupling protocol using Pd(OAc)2/SPhos/iPr2NEt catalysis displayed sufficient reactivity.
- 13 Lu G.-P. Voigtritter KR. Cai C. Lipshutz BH. J. Org. Chem. 2012; 77: 3700