Organocatalytic Asymmetric Tandem Cyclization/Michael Addition via Oxazol-5(2<i>H</i>)-One Formation: Access to Perfluoroalkyl-Containing <i>N</i>,<i>O</i>-Acetal Derivatives.
Li, Luyao; Yang, Tianxiao; Zhang, Tao; Zhu, Bo; Chang, Junbiao; The Journal of organic chemistry 85 (2020) 12294–12303; doi:10.1021/acs.joc.0c01545

data_4038795
_publ_section_title
;
 Organocatalytic Asymmetric Tandem Cyclization/Michael Addition via
 Oxazol-5(2<i>H</i>)-One Formation: Access to Perfluoroalkyl-Containing
 <i>N</i>,<i>O</i>-Acetal Derivatives.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12294
_journal_page_last               12303
_journal_paper_doi               10.1021/acs.joc.0c01545
_journal_volume                  85
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H21 F3 N2 O7'
_chemical_formula_sum            'C20 H21 F3 N2 O7'
_chemical_formula_weight         458.39
_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     iterative
_audit_creation_date             2019-09-24
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.13243(7)
_cell_length_b                   12.32391(16)
_cell_length_c                   29.4905(3)
_cell_measurement_reflns_used    16787
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      71.3620
_cell_measurement_theta_min      4.6650
_cell_volume                     2592.20(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      296(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.987
_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   -106.00 -44.00   1.00    1.31    --  -35.62-167.00 -77.00   62
  2  \w     47.00 109.00   1.00    1.31    --   35.62-167.00 -77.00   62
  3  \w     17.00 105.00   1.00    1.31    --   35.62  40.00 -64.00   88
  4  \w     99.00 177.00   1.00    5.25    --  107.12 116.00 156.00   78
  5  \w     65.00 159.00   1.00    5.25    --  107.12 167.00 -57.00   94
  6  \w     39.00 137.00   1.00    5.25    --  107.12 -83.00 -42.00   98
  7  \w     97.00 175.00   1.00    5.25    --  107.12  83.00  77.00   78
  8  \w     38.00 125.00   1.00    5.25    --  107.12 -40.00 141.00   87
  9  \w     55.00 108.00   1.00    1.31    --   35.62-178.00 -30.00   53
 10  \w      1.00  75.00   1.00    1.31    --   35.62 -99.00-120.00   74
 11  \w     57.00 108.00   1.00    1.31    --   35.62 178.00  60.00   51
 12  \w     55.00 108.00   1.00    1.31    --   35.62-178.00-150.00   53
 13  \w     38.00 110.00   1.00    5.25    --  107.12 -95.00 -90.00   72
 14  \w     39.00 125.00   1.00    5.25    --  107.12 -45.00-120.00   86
 15  \w     38.00 110.00   1.00    5.25    --  107.12 -95.00-150.00   72
 16  \w    100.00 177.00   1.00    5.25    --  107.12 111.00 -90.00   77
 17  \w      9.00 103.00   1.00    1.31    --   35.62  77.00-150.00   94
 18  \w     19.00 103.00   1.00    1.31    --   35.62  57.00 120.00   84
 19  \w      9.00 103.00   1.00    1.31    --   35.62  77.00  30.00   94
 20  \w      9.00 103.00   1.00    1.31    --   35.62  77.00 -30.00   94
 21  \w      9.00 103.00   1.00    1.31    --   35.62  77.00 150.00   94
 22  \w     69.00 178.00   1.00    5.25    --  107.12  15.00  30.00  109
 23  \w     80.00 175.00   1.00    5.25    --  107.12  77.00-180.00   95
 24  \w     86.00 177.00   1.00    5.25    --  107.12  30.00-120.00   91
 25  \w     80.00 175.00   1.00    5.25    --  107.12  77.00-120.00   95
 26  \w     86.00 177.00   1.00    5.25    --  107.12  30.00  90.00   91
 27  \w     90.00 176.00   1.00    5.25    --  107.12  45.00 -60.00   86
 28  \w     37.00 113.00   1.00    5.25    --  107.12-111.00 120.00   76
 29  \w     80.00 175.00   1.00    5.25    --  107.12  77.00 150.00   95
 30  \w     80.00 175.00   1.00    5.25    --  107.12  77.00  30.00   95
 31  \w     86.00 177.00   1.00    5.25    --  107.12  30.00 150.00   91
 32  \w    -62.00  32.00   1.00    1.31    --  -35.62  77.00  60.00   94
 33  \w    -55.00  34.00   1.00    1.31    --  -35.62  38.00 -30.00   89
 34  \w      9.00 103.00   1.00    1.31    --   35.62  77.00 -90.00   94
 35  \w      6.00 107.00   1.00    1.31    --   35.62  19.00 120.00  101
 36  \w    -34.00  55.00   1.00    1.31    --   35.62 -38.00 120.00   89
 37  \w     80.00 175.00   1.00    5.25    --  107.12  77.00 -60.00   95
 38  \w     80.00 175.00   1.00    5.25    --  107.12  77.00  90.00   95
 39  \w     80.00 175.00   1.00    5.25    --  107.12  77.00 120.00   95
 40  \w     86.00 177.00   1.00    5.25    --  107.12  30.00 -60.00   91
 41  \w     80.00 160.00   1.00    5.25    --  107.12  77.00 -30.00   80
 42  \w     80.00 175.00   1.00    5.25    --  107.12  77.00   0.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0848737000
_diffrn_orient_matrix_UB_12      -0.1046509000
_diffrn_orient_matrix_UB_13      -0.0197615000
_diffrn_orient_matrix_UB_21      -0.0690396000
_diffrn_orient_matrix_UB_22      -0.0329535000
_diffrn_orient_matrix_UB_23      0.0476069000
_diffrn_orient_matrix_UB_31      -0.1861770000
_diffrn_orient_matrix_UB_32      0.0597358000
_diffrn_orient_matrix_UB_33      -0.0087697000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0147
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            43311
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.622
_diffrn_reflns_theta_min         6.385
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.892
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81250
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.175
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.205
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1924 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     294
_refine_ls_number_reflns         4999
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.152
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0783P)^2^+0.2511P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1187
_refine_ls_wR_factor_ref         0.1207
_reflns_Friedel_coverage         0.736
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                4781
_reflns_number_total             4999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01545_si_002.cif
_cod_data_source_block           lly-20190728
_cod_depositor_comments          'Adding full bibliography for 4038795.cif.'
_cod_database_code               4038795
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 H1 O1 N1 F1'
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.893
_diffrn_oxdiff_digest_frames
;
015a0276730f4f93e12e9f02e1e6c6037500034a854
;
_diffrn_oxdiff_digest_hkl
;
0188e43b702b8366b9549467739c5ee0b3e144
;
_reflns_odcompleteness_completeness 99.89
_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. Rigid bond restraints
 C17, C18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C17) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Sof(N1B)=Sof(O6B)=Sof(O7B)=1-FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C9(H9)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11a,H11b), C13(H13a,H13b)
5.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C16(H16), C17(H17), C19(H19)
5.d Fitted hexagon refined as free rotating group:
 C20(C15,C16,C17,C18,C19)
5.e Idealised Me refined as rotating group:
 C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C4(H4a,H4b,H4c), C12(H12a,H12b,H12c)
;
_shelx_res_checksum              69866
_shelx_hkl_checksum              88653
_shelx_fab_checksum              59005
_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 1.210
_oxdiff_exptl_absorpt_empirical_full_min 0.833