Synlett 2018; 29(09): 1211-1214
DOI: 10.1055/s-0036-1591774
letter
© Georg Thieme Verlag Stuttgart · New York

Iron-Catalyzed Grignard Cross-Couplings with Allylic Methyl Ethers or Allylic Trimethylsilyl Ethers

Chika Seto
Department of Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, Japan   Email: [email protected]
,
Takeshi Otsuka
Department of Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, Japan   Email: [email protected]
,
Yoshiki Takeuchi
Department of Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, Japan   Email: [email protected]
,
Daichi Tabuchi
Department of Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, Japan   Email: [email protected]
,
Takashi Nagano*
Department of Chemistry, Faculty of Science, Kochi University, 2-5-1 Akebono-cho, Kochi 780-8520, Japan   Email: [email protected]
› Author Affiliations
This work was supported by JSPS KAKENHI Grant-in-Aid for Young Scientists (B) (Grant Number 25810064).
Further Information

Publication History

Received: 29 January 2018

Accepted after revision: 13 February 2018

Publication Date:
19 March 2018 (online)


Abstract

We have found that cross-coupling between aryl Grignard reagents and allylic methyl ethers proceeded well in the presence of a catalytic amounts of Fe(acac)3 to afford the corresponding allylic substitution products in good yields. Under the same conditions, allylic trimethylsilyl ethers also reacted with Grignard reagents to give the corresponding cross-coupling products.

Supporting Information

 
  • References and Notes

  • 1 Tamura M. Kochi JK. J. Am. Chem. Soc. 1971; 93: 1487

    • For reviews on iron-catalyzed cross-coupling reactions, see:
    • 2a Bolm C. Legros J. Le Paih J. Zani L. Chem. Rev. 2004; 104: 6217
    • 2b Fürstner A. Martin R. Chem. Lett. 2005; 34: 624
    • 2c Sherry BD. Fürstner A. Acc. Chem. Res. 2008; 41: 1500
    • 2d Czaplik WM. Mayer M. Cvengroš J. von Wangelin AJ. ChemSusChem 2009; 2: 396
    • 2e Nakamura E. Hatakeyama T. Ito S. Ishizuka K. Ilies L. Nakamura M. Org. React. (N. Y.) 2014; 83: 1
    • 2f Bauer I. Knölker H.-J. Chem. Rev. 2015; 115: 3170

      For pioneering works on iron-catalyzed allylic substitutions using soft carbon nucleophiles, see:
    • 3a Roustan JL. Mérour JY. Houlihan F. Tetrahedron Lett. 1979; 20: 3721
    • 3b Dieter J. Nicholas KM. J. Organomet. Chem. 1981; 212: 107
    • 3c Ladoulis SJ. Nicholas KM. J. Organomet. Chem. 1985; 285: C13
    • 3d Silverman GS. Strickland S. Nicholas KM. Organometallics 1986; 5: 2117
    • 3e Xu Y. Zhou B. J. Org. Chem. 1987; 52: 974
    • 3f Zhou B. Xu Y. J. Org. Chem. 1988; 53: 4419
    • 4a Yanagisawa A. Nomura N. Yamamoto H. Synlett 1991; 513
    • 4b Yanagisawa A. Nomura N. Yamamoto H. Tetrahedron 1994; 50: 6017
  • 5 Qui L. Ma E. Jia F. Li Z. Tetrahedron Lett. 2016; 57: 2211
    • 6a Nagano T. Hayashi T. Org. Lett. 2004; 6: 1297
    • 6b Nagano T. Hayashi T. Org. Lett. 2005; 7: 491
    • 6c Nagano T. Kobayashi S. Chem. Lett. 2008; 37: 1042

      For allylic substitution reaction of allylic ethers with aryl metal reagents catalyzed by other transition metals, see:
    • 7a Hayashi T. Konishi M. Yokota K.-i. Kumada M. J. Chem., Soc., Chem. Commun. 1981; 313
    • 7b Hayashi T. Konishi M. Yokota K.-i. Kumada M. J. Organomet. Chem. 1985; 285: 359
    • 7c Sugimura H. Takei H. Chem. Lett. 1985; 14: 351
    • 7d Chung K.-G. Miyake Y. Uemura S. J. Chem. Soc., Perkin Trans. 1 2000; 2725
    • 7e Mizutani K. Yorimitsu H. Oshima K. Chem. Lett. 2004; 33: 832
    • 7f Yasui H. Mizutani K. Yorimitsu H. Oshima K. Tetrahedron 2006; 62: 1410
    • 7g Tsukamoto H. Uchiyama T. Suzuki T. Kondo Y. Org. Biomol. Chem. 2008; 6: 3005
    • 7h Kiuchi H. Takahashi D. Funaki K. Sato T. Oi S. Org. Lett. 2012; 14: 4502
    • 7i Mino T. Kogure T. Abe T. Koizumi T. Fujita T. Sakamoto M. Eur. J. Org. Chem. 2013; 1501
  • 8 When we carried out the reaction of 1a with 2a under Li’s conditions (DCE–NMP, –13 °C, 1 h) (see Ref. 5), we observed the formation of 3aa in 19% yield (75% of 1a was recovered).
  • 9 The cross-coupling product 3ab (Table 2, entry 2) contained a small amount of an inseparable double-bond regioisomer, whereas the sample product 3ab prepared from the corresponding silyl ether (Scheme 6) did not contain this regioisomer (see Supporting Information). From these observations, we assume that an isomerization pathway from the normal coupling product to its double-bond regioisomer exists in the reaction system of the allylic methyl ether. A plausible mechanism is as follows. Oxidative addition of R–OMe to the low-valent iron species gives R–[Fe]–OMe. β-Hydrogen elimination from the methyl group results in the formation of an iron hydride species R–[Fe]–H. Insertion of olefin 3ab into the iron–hydride bond, followed by β-hydrogen elimination, affords the corresponding double-bond regioisomer.
  • 10 We also attempted to react 1a with Me(CH2)7MgBr (2i) under Li’s conditions (DCE–NMP, –15 °C, 1 h; Ref. 5), but the yield of 3ai was only 5% (76% of 1a was recovered.). With our catalyst system (Table 2, entry 9), 1a was fully consumed, and large amounts of (1E)-prop-1-en-1-ylbenzene were formed.
  • 11 The isolated mixture of (E)- and (Z)-3aa contained small amounts of the reductive homocoupling product PhCH=CH(CH2)2CH=CHPh (molar ratio: E/Z/homo = 84:13:3). This homocoupling product was inseparable from (Z)-3aa. See Supporting Information.
  • 12 The formation of the branched isomer b-3ba from the hexyl-substituted substrates 1b and 1b′ might be due to a decrease in steric repulsion.
  • 13 Similar results have been reported in nickel- or palladium-catalyzed allylic substitutions with Grignard reagents, although no detailed discussion has been reported on the difference between linear and branched substrates [see Refs. 7 (a) and 7 (b)].
  • 14 The formation of an Fe(I) species by the reaction of FeX3 with aryl Grignard reagents has been suggested; see: Hedström A. Lindstedt E. Norrby P.-O. J. Organomet. Chem. 2013; 748: 51

    • A similar discussion has been reported in the literature dealing with the nickel-catalyzed cross-coupling of allylic alcohols with Grignard reagents; see:
    • 15a Felkin H. Swierczewski G. Tetrahedron Lett. 1972; 13: 1433
    • 15b Felkin H. Swierczewski G. Tetrahedron 1975; 31: 2735
  • 16 The use of two equivalents of Grignard reagent resulted in a 69% yield of 3aa with an 8% yield of the reductive homocoupling product. In the case of the reaction with four equivalents of 2a (Scheme 5), the yield of the homocoupling product was 6%.
  • 17 We have previously reported an iron-catalyzed chemoselective cross-coupling with a bifunctional substrate possessing both aryl triflate and alkyl bromide moieties: see Ref. 6(a).
  • 18 Iron-Catalyzed Allylic Substitutions with Grignard Reagent; General Procedure To a solution of Fe(acac)3 (9.0 mg, 0.025 mmol, 5 mol%) in THF (1 mL) was added the appropriate allylic ether (0.5 mmol) and additional THF (4 mL). A ~1 M solution of the appropriate Grignard reagent in THF (1.0 mmol) was added, and the mixture was stirred for 4 h at rt. The reaction was quenched by the addition of 1 N aq HCl, and the resulting mixture was extracted with CH2Cl2. The combined organic layers were dried (MgSO4), filtered, and concentrated. The residue was purified by flash column chromatography or TLC on silica gel. 1,1′-(1E)-Prop-1-ene-1,3-diyldibenzene [(E)-3aa] Colorless oil; yield: 154 mg (79%). 1H NMR (500 MHz, CDCl3): δ = 7.36–7.28 (m, 10 H), 6.46 (d, J = 15.5 Hz, 1 H), 6.36 (dt, J = 15.5, 7.0 Hz, 1 H), 3.55 (d, J = 7.0 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 140.1, 137.4, 131.0, 129.2, 128.6, 128.5 (overlap), 127.1, 126.1, 126.1, 39.3. These NMR data are in agreement with those previously reported: see Ref. 7 (i).