Synlett 2017; 28(18): 2445-2448
DOI: 10.1055/s-0036-1590826
cluster
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Stereoselectively Functionalized Silacyclopentanes

Kazunobu Igawa*a, b, Akihiro Kuroob, Daisuke Yoshihirob, Yuki Yamanakab, Katsuhiko Tomooka*a, b
  • aInstitute for Materials Chemistry and Engineering and IRCCS, Kyushu University, Kasuga, Fukuoka 816-8580, Japan   Email: kigawa@cm.kyushu-u.ac.jp   Email: ktomooka@cm.kyushu-u.ac.jp
  • bDepartment of Molecular and Material Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan
This research was supported by JSPS KAKENHI Grants JP16K13955, JP15K13697, and 17H06235, Integrated Research Consortium on Chemical Sciences, the Cooperative Research Program of ‘Network Joint Research Center for Materials and Devices’, Kakihara Science Technology Foundation, and Ube Industries Foundation.
Further Information

Publication History

Received: 16 May 2017

Accepted: 12 June 2017

Publication Date:
25 August 2017 (eFirst)

Dedicated to Professor Teruaki Mukaiyama in celebration of his 90th birthday (Sotsuju)

Published as part of the Cluster Silicon in Synthesis and Catalysis

Abstract

An efficient approach to a variety of chiral silacyclopentanes having silicon stereogenic center based on the stereospecific transformations of C4 carbon stereogenic center of silacyclopentenols by ­Mitsunobu reaction or Tsuji–Trost reaction has been developed. The thus obtained substitution products can be converted into novel silacyclopentane triols, amines, and carboxylic acids in stereospecific manner.

Supporting Information

 
  • References and Notes

  • 1 Brook MA. Silicon in Organic, Organometallic, and Polymer Chemistry . John Wiley and Sons; New York; 2000
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    • Recent reports on stereoselective synthesis of chiral silicon molecules:
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  • 7 Mitsunobu O. Synthesis 1981; 1
  • 8 Selected Crystal Data for (S Si*,4R*)-4a in Racemic Form Triclinic, P–1 (No. 2), a = 6.619(3) Å, b = 7.239(4) Å, c = 21.720(12) Å, α = 86.28(5)°, β = 84.55(4)°, γ = 73.97(3)°, V = 994.9(9) Å3, Z = 2, R1 = 0.1460, wR2 = 0.1916, CCDC 1546493.
  • 9 General Procedure for Mitsunobu Reaction of Silacyclopentenol 3 To a solution of (S Si,4S)-3a (20.0 mg, 0.0860 mmol) in toluene (2 mL) was added PPh3 (33.9 mg, 0.129 mmol), p-nitrobenzoic acid (17.3 mg, 0.104 mmol), and DEAD (58.7 μL of 2.20 M solution in toluene, 0.129 mmol) at rt and stirred for 6 h. The solvent of the reaction mixture was removed under reduced pressure. The crude product was purified by silica gel column chromatography (hexane/EtOAc = 50:1 to 30:1) to afford 27.5 mg (84%) of (S Si,4R)-4a as a colorless crystal and 2.3 mg (12%) of 5 as a colorless oil, respectively. Compound Data of (S Si,4R)-4a 1H NMR (300 MHz, CDCl3): δ = 8.32–8.21 (m, 4 H), 7.55–7.21 (m, 2 H), 7.41–7.34 (m, 3 H), 6.94 (dd, J = 10.2, 2.1 Hz, 1 H), 6.53 (dd, J = 10.2, 1.8 Hz, 1 H), 6.01–5.95 (m, 1 H), 1.85 (dd, J = 15.3, 8.1 Hz, 1 H), 1.14 (dd, J = 15.3, 5.7 Hz, 1 H), 1.02 (s, 9 H). 13C NMR (75 MHz, CDCl3): δ = 164.4, 152.2, 150.6, 136.1, 134.9, 134.5, 131.9, 130.8, 129.5, 127.9, 123.6, 80.0, 26.9, 17.2, 14.6. IR (reflection): 2928, 1711, 1523, 1343, 1104, 901, 714, 638, 602, 520 cm–1. HRMS (EI, positive): m/z calcd for C17H14NO4Si [M – tBu]+, requires m/z: 324.0692; found: 324.0688. [α]D 26 –158.3 (c 1.02, CHCl3) for >98% ee.

    • Silyl substituent effect on regioselective ring opening of epoxide, see:
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    • 10b Manuel G. Boukherroub R. J. Organomet. Chem. 1993; 447: 167

      Study on stereoselectivity of Tsuji–Trost reaction, see:
    • 11a Hayashi T. Hagihara T. Konishi M. Kumada M. J. Am. Chem. Soc. 1983; 105: 7767
    • 11b Murahashi S.-I. Taniguchi Y. Imada Y. Tanigawa Y. J. Org. Chem. 1989; 54: 3292
    • 11c Granberg KL. Bäckvall J.-E. J. Am. Chem. Soc. 1992; 114: 6858
  • 12 General Procedure for Tsuji–Trost Reaction of Methyl Carbonate 12 To a solution of dimethyl malonate (21.7 μL, 0.189 mmol) in THF (2 mL) was added NaH (63% in mineral oil, 7.2 mg, 0.189 mmol) at rt. After stirring for 20 min, to this solution was added P(o-tolyl)3 (7.2 mg, 23.7 μmol), Pd2(dba)3·CHCl3 (4.9 mg, 4.73 μmol), and a solution of carbonate (S Si,4S)-12a (27.4 mg, 0.0943 mmol) in THF (1 mL) at that temperature, then stirred for 6.5 h at 50 °C. The reaction was quenched with sat. aq. NH4Cl, then extracted with Et2O. The combined organic phases were dried over Na2SO4, filtered, and the solvent was removed under reduced pressure. The crude product was purified by silica gel chromatography (hexane/Et2O = 20:1) to afford 21.0 mg (64%) of (S Si,4S)-13a as a colorless oil. IR (neat): 2953, 2855, 1738, 1435, 1200, 1142, 1008, 823, 730, 525 cm–1. Compound Data of (S Si,4S)-13a 1H NMR (300 MHz, CDCl3): δ = 7.51–7.48 (m, 2 H), 7.36–7.31 (m, 3 H), 6.81 (dd, J = 9.9, 1.8 Hz, 1 H), 6.30 (dd, J = 9.9, 2.4 Hz, 1 H), 3.65 (s, 3 H), 3.63 (s, 3 H), 3.54–3.44 (m, 1 H), 3.28 (d, J = 9.0 Hz, 1 H), 1.36 (dd, J = 15.3, 8.4 Hz, 1 H), 0.93 (s, 9 H), 0.71 (dd, J = 15.3, 6.0 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 169.0, 154.8, 136.5, 134.6, 129.1, 128.8, 127.7, 58.3, 52.4, 44.9, 26.7, 17.8, 10.6. HRMS (FAB, matrix: m-nitrobenzyl alcohol, positive): m/z calcd for C15H17O4Si [M –tBu]+ requires 289.0896; found: 289.0897. [α]D 21 +33.3 (c 0.20, CHCl3) for >98% ee.