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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2015, Vol. 9 Issue (3) : 359-368    https://doi.org/10.1007/s11705-015-1530-6
RESEARCH ARTICLE
Fluoroalcohol-mediated reductive iodonio-Claisen rearrangement: Synthesis of complex ortho-substituted-allyl iodoarenes? ?
Hem Raj Khatri,Hai Nguyen,James K. Dunaway,Jianglong Zhu()
Department of Chemistry and Biochemistry and School of Green Chemistry and Engineering, The University of Toledo, Toledo, OH 43606, USA
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Abstract

Reductive iodonio-Claisen rearrangement (RICR) involving λ3-iodanes and allyl or substituted-allyl silanes in fluoroalcohols, such as 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE), was studied for the synthesis of complex ortho-allyl or substituted-allyl iodoarenes. In comparison to the previously reported condition involving boron trifluoride diethyl etherate, the RICR mediated by fluoroalcohols was found to proceed more effectively. The resulting complex ortho-allyl iodoarenes are useful synthetic intermediates and can be readily converted to various heterocyclic compounds.
Keywords hypervalent iodine      allylation      fluoroalcohol      Claisen rearrangement      heterocycles     
Corresponding Author(s): Jianglong Zhu   
Online First Date: 10 September 2015    Issue Date: 30 September 2015
 Cite this article:   
James K. Dunaway,Jianglong Zhu,Hem Raj Khatri, et al. Fluoroalcohol-mediated reductive iodonio-Claisen rearrangement: Synthesis of complex ortho-substituted-allyl iodoarenes? ?[J]. Front. Chem. Sci. Eng., 2015, 9(3): 359-368.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-015-1530-6
https://academic.hep.com.cn/fcse/EN/Y2015/V9/I3/359
Fig.1  Scheme 1 Synthesis of ortho-allyl or substituted-allyl iodoarenes via reductive iodonio-Claisen rearrangement
Entry Promoter Solventa) 8 : 9 : 10b) Yield of 8c)
1 BF3·Et2O CH2Cl2/CH3CN (1/1, v/v), −50 °Cd) 2.22/0.45/1.0 N.D.
2 BF3·Et2O CH2Cl2, −80 °Cd) 0.5/0.09/1.0 N.D.
3 BF3·Et2O CH2Cl2, −25 °Cd) 0.78/0.23/1.0 N.D.
4 None HFIP, 0 °Ce) 1.85/0.53/1.0 N.D.
5 None HFIP/CH2Cl2(1/1, v/v), −20 °Cf) 1.0/0.32/1.0 N.D.
6 None TFE, −40 °Ce) 4.76/1.57/1.0 60%
Tab.1  Reaction optimization for the synthesis of ortho-methallyliodoarene 8
Fig.3  Scheme 2 RICRs involving complex λ3-iodanes and methallyltrimethylsilane in fluoroalcohol
Fig.4  Scheme 3 RICRs involving complex λ3-iodanes and prenyltrimethylsilane or crotylsilanes in HFIP
Entry λ3-iodanes Reaction conditions
HFIP, 0 °C????? TFE, ?40 °C??????
2 : 20 : 10 b) Yield c) 2 : 20 : 10 b) Yieldc)
1 1a 9.0 : 4.0 : 1.0 77 % (53%) 13 : 4.1 : 1.0 88 % (67%)
2 1b 11.3 : 0.0 : 1.0 (77%) 20 : 0.0 : 1.0 (90%)
3 1c 4.34 : 0.65 : 1.0 66 % (57%) 4.76 : 1.52 : 1.0 78 % (59%)
4 1d 7.5 : trace : 1.0 (71%) 4.0 : trace : 1.0 (70%)
5 1e 19.4 : trace : 1.0 (82%) 20 : trace : 1.0 (88%)
6 1f 11.75 : 0.0 : 1.0 (74%) 6.0 : 0.0 : 1.0 (75%)
7 1g 4.34 : 0.0 : 1.0 (80%) 4.4 : 0.0 : 1.0 (73%)
Tab.2  Reinvestigation of RICR involving allyltrimethylsilane in fluoroalcoholsa)
Fig.6  Scheme 4 Synthesis of various heterocycles from o-allyliodoarenes. (a) 1.25 mol-% OsO4, K3[Fe(CN)6], K2CO3, tBuOH/H2O. (b) TBDPSCl, imidazole, DMF. (c) 10 mol-% Pd(OAc)2, 12 mol-% rac-2-(di-t-butylphosphino)-1,1'-binaphthyl, Cs2CO3, toluene. (d) PhCH(OMe)2, 10 mol-% p-TsOH, benzene. (e) DIBAL-H, CH2Cl2, −78 to 0 °C. (f) NaIO4, THF/H2O. (g) BnNH2, HOAc, NaBH(OAc)3, EtOH. (h) 5 mol-% CuI, 20 mol-% 2-isobutyrylcyclohexanone, DMF. (i) 1.25 mol-% OsO4, NaIO4, THF/H2O. (j) 10 mol-% CuI, K3PO4, DMF
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