Copper-catalyzed α-C–H amidation of simple ethers through C(sp3)–H/N–H cross dehydrogenative coupling
Yue, Qiang; Xiao, Zhen; Ran, Ziyao; Yuan, Songdong; Zhang, Qian; Li, Dong; Organic Chemistry Frontiers 5 (2018) 967–; doi:10.1039/C7QO01003F

data_1553947
_publ_section_title
;
 Copper-catalyzed \a-C--H amidation of simple ethers through
 C(sp3)--H/N--H cross dehydrogenative coupling
;
_journal_issue                   6
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              967
_journal_paper_doi               10.1039/C7QO01003F
_journal_volume                  5
_journal_year                    2018
_chemical_formula_moiety         'C16 H18 N2 O2'
_chemical_formula_sum            'C16 H18 N2 O2'
_chemical_formula_weight         270.32
_chemical_name_systematic
N-(8-quinolyl)-N-(2-tetrahydrofuranyl)propionamide
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-04-09
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5335)
;
_audit_update_record
;
2017-07-28 deposited with the CCDC.
2017-12-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.577(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5527(3)
_cell_length_b                   12.3620(5)
_cell_length_c                   12.0679(5)
_cell_measurement_reflns_used    1685
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.2470
_cell_measurement_theta_min      3.6620
_cell_volume                     1423.66(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w      4.00  36.00   1.00    1.50    --  -33.50  19.00-180.00   32
  2  \w    -67.00 -41.00   1.00    1.50    --  -33.50 178.00-120.00   26
  3  \w    -69.00 -30.00   1.00    1.50    --  -33.50  19.00-180.00   39
  4  \w   -101.00 -75.00   1.00    1.50    --  -33.50 178.00-120.00   26
  5  \w    -35.00   7.00   1.00    1.50    --  -33.50  37.00-120.00   42
  6  \w     69.00  99.00   1.00    1.50    --   36.47  57.00 120.00   30
  7  \w     42.00  68.00   1.00    1.50    --   36.47 -99.00  30.00   26
  8  \w     26.00  59.00   1.00    1.50    --   36.47 -77.00  60.00   33
  9  \w    -33.00  11.00   1.00    1.50    --   36.47 -77.00  60.00   44
 10  \w     -3.00  63.00   1.00    1.50    --   36.47 -99.00 -90.00   66
 11  \w     -2.00  32.00   1.00    1.50    --   36.47 -99.00  30.00   34
 12  \w     61.00  87.00   1.00    7.50    --  108.00 -30.00 -90.00   26
 13  \w     41.00  99.00   1.00    7.50    --  108.00 -45.00 -30.00   58
 14  \w     39.00  81.00   1.00    7.50    --  108.00 -30.00  90.00   42
 15  \w     65.00  91.00   1.00    7.50    --  108.00 -30.00 -30.00   26
 16  \w     67.00 115.00   1.00    7.50    --  108.00-111.00 -90.00   48
 17  \w     40.00 106.00   1.00    7.50    --  108.00 -94.00 150.00   66
 18  \w     68.00 107.00   1.00    7.50    --  108.00 -94.00   0.00   39
 19  \w     39.00  91.00   1.00    7.50    --  108.00 -30.00-120.00   52
 20  \w     54.00  91.00   1.00    7.50    --  108.00 -30.00 120.00   37
 21  \w     45.00  88.00   1.00    7.50    --  108.00 -45.00-180.00   43
 22  \w     55.00 145.00   1.00    7.50    --  108.00   0.00  90.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0375184000
_diffrn_orient_matrix_UB_12      0.1183587000
_diffrn_orient_matrix_UB_13      0.0280388000
_diffrn_orient_matrix_UB_21      0.0368623000
_diffrn_orient_matrix_UB_22      -0.0325846000
_diffrn_orient_matrix_UB_23      0.1209634000
_diffrn_orient_matrix_UB_31      0.1528015000
_diffrn_orient_matrix_UB_32      -0.0212535000
_diffrn_orient_matrix_UB_33      -0.0302050000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0228
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            5395
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.968
_diffrn_reflns_theta_max         66.968
_diffrn_reflns_theta_min         5.125
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.675
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       prism
_exptl_crystal_F_000             576
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.154
_refine_diff_density_rms         0.030
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         2542
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0480
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0686P)^2^+0.1687P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1289
_refine_ls_wR_factor_ref         0.1442
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1892
_reflns_number_total             2542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7qo01003f2.cif
_cod_data_source_block           20170446
_cod_original_cell_volume        1423.66(10)
_cod_database_code               1553947
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C38H70N2O2
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C12-C11 = C12A-C11A = C13-C12 = C10-C11A = C11-C10
 1.55 with sigma of 0.02
 C10-O1 = C10-O1A = O1-C13 = O1A-C13A
 1.43 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C12) = Uanis(C12A)
Uanis(C11) = Uanis(C11A)
Uanis(C13) = Uanis(C13A)
Uanis(O1) = Uanis(O1A)
Uanis(O2) = Uanis(O2A)
4. Others
 Sof(H10A)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(O1A)=1-FVAR(1)
 Sof(H10)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=
 Sof(H13A)=Sof(H13B)=Sof(O1)=FVAR(1)
 Sof(O2A)=1-FVAR(2)
 Sof(O2)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C10(H10), C10(H10A)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C11A(H11C,H11D), C12(H12A,H12B), C12A(H12C,H12D), C13(H13A,
 H13B), C13A(H13C,H13D), C15(H15A,H15B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C7(H7), C8(H8), C9(H9)
5.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.261
_oxdiff_exptl_absorpt_empirical_full_min 0.852