Divergent functionalization of α,β-enones: catalyst-free access to β-azido ketones and β-amino α-diazo ketones.
Tu, Youshao; Dong, Honglin; Wang, Huamin; Ao, Yuhui; Liu, Yu; Chemical communications (Cambridge, England) 57 (2021) 4524–4527; doi:10.1039/d1cc00985k

data_7128112
_publ_section_title
;
 Divergent functionalization of \a,\b-enones: catalyst-free access to
 \b-azido ketones and \b-amino \a-diazo ketones.
;
_journal_issue                   37
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              4524
_journal_page_last               4527
_journal_paper_doi               10.1039/d1cc00985k
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C14 H10 F3 N3 O'
_chemical_formula_sum            'C14 H10 F3 N3 O'
_chemical_formula_weight         293.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-07 deposited with the CCDC.	2021-03-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.65470(10)
_cell_length_b                   8.3977(2)
_cell_length_c                   21.0738(4)
_cell_measurement_reflns_used    7735
_cell_measurement_temperature    292.62(10)
_cell_measurement_theta_max      73.2550
_cell_measurement_theta_min      5.6610
_cell_volume                     1354.66(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292.62(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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    -35.00  16.00   1.00    1.00    --    0.00 -38.00  60.00   51
  2  \w    -36.00  19.00   1.00    1.00    --    0.00 -38.00 120.00   55
  3  \w    -87.00 -51.00   1.00    1.00    --    0.00 -38.00 -30.00   36
  4  \w    -87.00 -47.00   1.00    1.00    --    0.00 -38.00  60.00   40
  5  \w    -85.00 -50.00   1.00    1.00    --    0.00 -38.00 120.00   35
  6  \w    -26.00  18.00   1.00    1.00    --    0.00 -38.00 -30.00   44
  7  \w     84.00 114.00   1.00    1.00    --   95.80 -30.00 -60.00   30
  8  \w      6.00  43.00   1.00    1.00    --   95.80 -30.00 -60.00   37
  9  \w     43.00 128.00   1.00    1.00    --   95.80 -82.00 -90.00   85
 10  \w     44.00  71.00   1.00    1.00    --   95.80 -82.00   0.00   27
 11  \w     90.00 122.00   1.00    1.00    --   95.80 -82.00   0.00   32
 12  \w     86.00 128.00   1.00    1.00    --   95.80 -82.00-180.00   42
 13  \w     44.00 116.00   1.00    1.00    --   95.80 -45.00 150.00   72
 14  \w      7.00  57.00   1.00    1.00    --   95.80 -30.00 -30.00   50
 15  \w     77.00 174.00   1.00    1.00    --   95.80  30.00 -90.00   97
 16  \w     69.00 111.00   1.00    1.00    --   95.80 -30.00 -30.00   42
 17  \w     16.00 107.00   1.00    1.00    --   95.80 -61.00 120.00   91
 18  \w      7.00  33.00   1.00    1.00    --   95.80 -82.00-180.00   26
 19  \w      6.00 118.00   1.00    1.00    --   95.80 -82.00 120.00  112
 20  \w    146.00 171.00   1.00    1.00    --   95.80  30.00-120.00   25
 21  \w     27.00  53.00   1.00    1.00    --   95.80 -82.00 -60.00   26
 22  \w     60.00 124.00   1.00    1.00    --   95.80 -82.00 -60.00   64
 23  \w      6.00  74.00   1.00    1.00    --   95.80 -82.00 -30.00   68
 24  \w     99.00 124.00   1.00    1.00    --   95.80 -82.00 -30.00   25
 25  \w    106.00 183.00   1.00    1.00    --   95.80  30.00-180.00   77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0123917000
_diffrn_orient_matrix_UB_12      0.1017106000
_diffrn_orient_matrix_UB_13      0.0606315000
_diffrn_orient_matrix_UB_21      0.0043145000
_diffrn_orient_matrix_UB_22      -0.1525624000
_diffrn_orient_matrix_UB_23      0.0405576000
_diffrn_orient_matrix_UB_31      0.2009329000
_diffrn_orient_matrix_UB_32      -0.0030181000
_diffrn_orient_matrix_UB_33      -0.0046226000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            12707
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.073
_diffrn_reflns_theta_max         67.073
_diffrn_reflns_theta_min         4.196
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.058
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58969
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.175
_refine_diff_density_min         -0.124
_refine_diff_density_rms         0.024
_refine_ls_abs_structure_details
;
 Flack x determined using 893 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.40(7)
_refine_ls_extinction_coef       0.0032(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     191
_refine_ls_number_reflns         2394
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0302
_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^)+(0.0452P)^2^+0.1113P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0831
_refine_ls_wR_factor_ref         0.0842
_reflns_Friedel_coverage         0.700
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                2283
_reflns_number_total             2394
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc00985k2.cif
_cod_data_source_block           exp_1461
_cod_depositor_comments          'Adding full bibliography for 7128112.cif.'
_cod_database_code               7128112
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.45
_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
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C9(H9), C8(H8), C6(H6), C4(H4), C5(H5)
;
_shelx_res_checksum              17521
_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 3.490
_oxdiff_exptl_absorpt_empirical_full_min 0.460