Catalytic Chemo- and Regioselective Coupling of 1,3-Dicarbonyls with N-Heterocyclic Nucleophiles.
Kenny, Miles; Kitson, Daniel J.; Franckevičius, Vilius; The Journal of organic chemistry 81 (2016) 5162–5172; doi:10.1021/acs.joc.6b00731

data_4036860
_publ_section_title
;
 Catalytic Chemo- and Regioselective Coupling of 1,3-Dicarbonyls with
 N-Heterocyclic Nucleophiles.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5162
_journal_page_last               5172
_journal_paper_doi               10.1021/acs.joc.6b00731
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C22 H25 N O4'
_chemical_formula_sum            'C22 H25 N O4'
_chemical_formula_weight         367.43
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                87.781(3)
_cell_angle_beta                 84.683(3)
_cell_angle_gamma                82.145(3)
_cell_formula_units_Z            2
_cell_length_a                   7.6750(3)
_cell_length_b                   10.0757(4)
_cell_length_c                   12.4531(5)
_cell_measurement_reflns_used    16067
_cell_measurement_temperature    179.98(10)
_cell_measurement_theta_max      77.0770
_cell_measurement_theta_min      3.5860
_cell_volume                     949.54(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2303
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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   -110.00 -18.00   1.00    1.00    --  -38.50 -38.00-120.00   92
  2  \w   -110.00 -18.00   1.00    1.00    --  -38.50 -38.00 150.00   92
  3  \w    -92.00  -2.00   1.00    1.00    --  -38.50 125.00 -60.00   90
  4  \w    -29.00  72.00   1.00    1.00    --   42.14 -77.00  90.00  101
  5  \w     23.00  96.00   1.00    1.00    --   42.14-125.00-150.00   73
  6  \w     31.00 109.00   1.00    1.40    --  111.00 -94.00 150.00   78
  7  \w     38.00 132.00   1.00    1.40    --  111.00 -30.00 -30.00   94
  8  \w     38.00 132.00   1.00    1.40    --  111.00 -30.00 150.00   94
  9  \w     38.00 116.00   1.00    1.40    --  111.00-111.00 -60.00   78
 10  \w     38.00 116.00   1.00    1.40    --  111.00-111.00-180.00   78
 11  \w     90.00 178.00   1.00    1.40    --  111.00  30.00 -90.00   88
 12  \w     31.00 109.00   1.00    1.40    --  111.00 -94.00-150.00   78
 13  \w     89.00 178.00   1.00    1.40    --  111.00  45.00   0.00   89
 14  \w    100.00 178.00   1.00    1.40    --  111.00 111.00   0.00   78
 15  \w     38.00 116.00   1.00    1.40    --  111.00-111.00  30.00   78
 16  \w     41.00 133.00   1.00    1.40    --  111.00 -45.00  60.00   92
 17  \w     38.00 116.00   1.00    1.40    --  111.00-111.00 120.00   78
 18  \w     31.00 109.00   1.00    1.40    --  111.00 -94.00  60.00   78
 19  \w     43.00 137.00   1.00    1.40    --  111.00 -61.00-150.00   94
 20  \w    100.00 178.00   1.00    1.40    --  111.00 111.00-150.00   78
 21  \w     90.00 178.00   1.00    1.40    --  111.00  30.00 -30.00   88
 22  \w     40.00 141.00   1.00    1.40    --  111.00 -77.00 -60.00  101
 23  \w    -59.00  33.00   1.00    1.00    --  -38.50  38.00 -60.00   92
 24  \w     12.00 113.00   1.00    1.00    --   42.14  77.00  60.00  101
 25  \w     17.00 111.00   1.00    1.00    --   42.14  57.00   0.00   94
 26  \w     12.00 113.00   1.00    1.00    --   42.14  77.00 150.00  101
 27  \w     12.00 113.00   1.00    1.00    --   42.14  77.00-120.00  101
 28  \w     89.00 178.00   1.00    1.40    --  111.00  45.00  90.00   89
 29  \w     85.00 178.00   1.00    1.40    --  111.00  61.00 150.00   93
 30  \w     90.00 178.00   1.00    1.40    --  111.00  30.00 150.00   88
 31  \w     85.00 178.00   1.00    1.40    --  111.00  61.00-150.00   93
 32  \w     85.00 178.00   1.00    1.40    --  111.00  61.00  90.00   93
 33  \w     85.00 178.00   1.00    1.40    --  111.00  61.00 -90.00   93
 34  \w     81.00 178.00   1.00    1.40    --  111.00  77.00  90.00   97
 35  \w     85.00 178.00   1.00    1.40    --  111.00  61.00  60.00   93
 36  \w     81.00 178.00   1.00    1.40    --  111.00  77.00 -60.00   97
 37  \w     85.00 178.00   1.00    1.40    --  111.00  61.00-180.00   93
 38  \w     85.00 178.00   1.00    1.40    --  111.00  61.00  30.00   93
 39  \w     81.00 178.00   1.00    1.40    --  111.00  77.00 -90.00   97
 40  \w     81.00 178.00   1.00    1.40    --  111.00  77.00-150.00   97
 41  \w     81.00 178.00   1.00    1.40    --  111.00  77.00   0.00   97
 42  \w     90.00 178.00   1.00    1.40    --  111.00  30.00-150.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1182615000
_diffrn_orient_matrix_UB_12      -0.0992996000
_diffrn_orient_matrix_UB_13      0.0681237000
_diffrn_orient_matrix_UB_21      -0.0990726000
_diffrn_orient_matrix_UB_22      -0.1146729000
_diffrn_orient_matrix_UB_23      -0.0295377000
_diffrn_orient_matrix_UB_31      0.1325833000
_diffrn_orient_matrix_UB_32      -0.0288022000
_diffrn_orient_matrix_UB_33      -0.0996693000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0212
_diffrn_reflns_av_unetI/netI     0.0113
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            23526
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.437
_diffrn_reflns_theta_min         3.566
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.713
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91117
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (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    1.285
_exptl_crystal_description       prism
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.341
_exptl_crystal_size_mid          0.294
_exptl_crystal_size_min          0.251
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         3986
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0416
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0528P)^2^+0.3175P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1085
_refine_ls_wR_factor_ref         0.1101
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3758
_reflns_number_total             3986
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b00731_si_002.cif
_cod_data_source_block           vf101
_cod_original_cell_volume        949.54(6)
_cod_database_code               4036860
_chemical_oxdiff_formula         'C22 H25 N1 O4'
_chemical_oxdiff_usercomment     MK250
_reflns_odcompleteness_completeness 99.97
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C1A) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
3. Others
 Sof(H2BC)=Sof(H2BD)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(H2AA)=Sof(H2AB)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C2(H2AA,H2AB), C2(H2BC,H2BD), C12(H12A,H12B), C17(H17A,H17B), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C8(H8), C9(H9), C10(H10)
4.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C22(H22A,H22B,H22C), C1A(H1AA,H1AB,H1AC)
;
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-11-27
_olex2_exptl_crystal_mounting_method
'mounted on a polyimide loop using Paratone-N oil'
_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 1.148
_oxdiff_exptl_absorpt_empirical_full_min 0.881