Modular synthesis of aryl amines from 3-alkynyl-2-pyrones.
Gardner, Kristen E.; de Lescure, Louis; Hardy, Melissa A.; Tan, Jin; Sigman, Matthew S.; Paton, Robert S.; Sarpong, Richmond; Chemical science 15 (2024) 15632–15638; doi:10.1039/d4sc04885g

data_1572421
_publ_section_title
;
 Modular synthesis of aryl amines from 3-alkynyl-2-pyrones.
;
_journal_issue                   38
_journal_name_full               'Chemical science'
_journal_page_first              15632
_journal_page_last               15638
_journal_paper_doi               10.1039/d4sc04885g
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C22 H21 N O'
_chemical_formula_sum            'C22 H21 N O'
_chemical_formula_weight         315.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-03-09 deposited with the CCDC.	2024-08-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7760(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.86970(10)
_cell_length_b                   14.3822(2)
_cell_length_c                   9.93520(10)
_cell_measurement_reflns_used    13503
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.1270
_cell_measurement_theta_min      4.8150
_cell_volume                     1687.45(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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     37.00  63.00   0.50    0.50    --   50.96  57.00-120.00   52
  2  \w     91.00 125.00   0.50    0.50    --   50.96  77.00-180.00   68
  3  \w    107.00 163.00   0.50    0.50    --  107.75  61.00-180.00  112
  4  \w     39.00  97.00   0.50    0.50    --  107.75 -77.00 -90.00  116
  5  \w     40.00  88.00   0.50    0.50    --  107.75 -77.00  30.00   96
  6  \w     36.00  68.00   0.50    0.50    --  107.75 -61.00  60.00   64
  7  \w     40.00  68.00   0.50    0.50    --  107.75 -61.00  90.00   56
  8  \w     36.00  66.00   0.50    0.50    --  107.75 -61.00 150.00   60
  9  \w     39.00  67.00   0.50    0.50    --  107.75 -61.00 -90.00   56
 10  \w     41.00  67.00   0.50    0.50    --  107.75 -61.00-180.00   52
 11  \w     65.00  90.00   0.50    0.50    --  107.75-169.00-148.00   50
 12  \w     74.00 100.00   0.50    0.50    --  107.75-111.00-150.00   52
 13  \w     31.00  56.00   0.50    0.50    --  107.75-111.00-150.00   50
 14  \w     10.00  94.00   0.50    0.50    --   50.96-115.00  -4.00  168
 15  \w     70.00  95.00   0.50    0.50    --  107.75-115.00  -4.00   50
 16  \w     77.00 104.00   0.50    0.50    --  107.75 -94.00 -60.00   54
 17  \w     74.00 100.00   0.50    0.50    --  107.75 -94.00   0.00   52
 18  \w     73.00 106.00   0.50    0.50    --  107.75 -94.00  30.00   66
 19  \w     33.00  59.00   0.50    0.50    --  107.75 -94.00   0.00   52
 20  \w     75.00 109.00   0.50    0.50    --  107.75-111.00 150.00   68
 21  \w   -124.00 -82.00   0.50    0.50    --  -50.96 -77.00  30.00   84
 22  \w   -173.00 -88.00   0.50    0.50    -- -100.00 -94.00 -30.00  170
 23  \w    -70.00 -45.00   0.50    0.50    -- -100.00  61.00 150.00   50
 24  \w    -52.00 -26.00   0.50    0.50    -- -100.00  45.00  30.00   52
 25  \w    -52.00 -26.00   0.50    0.50    -- -100.00  45.00 -90.00   52
 26  \w    -54.00 -29.00   0.50    0.50    -- -100.00  45.00-150.00   50
 27  \w    -52.00 -26.00   0.50    0.50    -- -100.00  45.00-180.00   52
 28  \w    -54.00 -25.00   0.50    0.50    -- -100.00  45.00-120.00   58
 29  \w    -53.00 -26.00   0.50    0.50    -- -100.00  45.00 -60.00   54
 30  \w    -43.00  12.00   0.50    0.50    --  -50.96  38.00   0.00  110
 31  \w    -51.00 -26.00   0.50    0.50    -- -100.00  45.00  60.00   50
 32  \w    -46.00  24.00   0.50    0.50    --  -50.96  38.00 120.00  140
 33  \w    -94.00 -16.00   0.50    0.50    --  -50.96 115.00  85.00  156
 34  \w   -110.00 -23.00   0.50    0.50    -- -100.00 115.00  85.00  174
 35  \w    -89.00 -53.00   0.50    0.50    --  -50.96 125.00-180.00   72
 36  \w     46.00 128.00   0.50    0.50    --   50.96 169.00-130.00  164
 37  \w     55.00 105.00   0.50    0.50    --  107.75 169.00-130.00  100
 38  \w     81.00 149.00   0.50    0.50    --  107.75 115.00  85.00  136
 39  \w     81.00 127.00   0.50    0.50    --   50.96 115.00  85.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0059027000
_diffrn_orient_matrix_UB_12      0.0803415000
_diffrn_orient_matrix_UB_13      0.1016263000
_diffrn_orient_matrix_UB_21      -0.0252350000
_diffrn_orient_matrix_UB_22      0.0687423000
_diffrn_orient_matrix_UB_23      -0.1180677000
_diffrn_orient_matrix_UB_31      -0.1278573000
_diffrn_orient_matrix_UB_32      -0.0172639000
_diffrn_orient_matrix_UB_33      0.0027109000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            19025
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.445
_diffrn_reflns_theta_min         3.743
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74274
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.109a (Rigaku Oxford Diffraction, 2021)
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    1.241
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         3443
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0489P)^2^+0.6659P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0970
_refine_ls_wR_factor_ref         0.0983
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3240
_reflns_number_total             3443
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04885g4.cif
_cod_data_source_block           KGardner01_Sarpong
_cod_depositor_comments          'Adding full bibliography for 1572421.cif.'
_cod_database_code               1572421
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C N O H'
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.858
_diffrn_oxdiff_digest_frames
;
0189b980bc9559715e807078e2184b5b7d03210be3c
;
_diffrn_oxdiff_digest_hkl
;
01b7986a3cfb7ba85273612beffaa35ede63c6
;
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
;
_shelx_res_checksum              92188
_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 2.107
_oxdiff_exptl_absorpt_empirical_full_min 0.704