Palladium-Catalyzed Cascade Difluoroalkylation/Cyclization of N-Propargylamides: Synthesis of Oxazoles and Oxazolines.
Ma, Jun-Wei; Wang, Qiang; Wang, Xin-Gang; Liang, Yong-Min; The Journal of organic chemistry 83 (2018) 13296–13307; doi:10.1021/acs.joc.8b02111

data_4035770
_publ_section_title
;
 Palladium-Catalyzed Cascade Difluoroalkylation/Cyclization of
 N-Propargylamides: Synthesis of Oxazoles and Oxazolines.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13296
_journal_page_last               13307
_journal_paper_doi               10.1021/acs.joc.8b02111
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C15 H15 Cl F2 N2 O3'
_chemical_formula_sum            'C15 H15 Cl F2 N2 O3'
_chemical_formula_weight         344.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-03-28
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 112.004(6)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   17.4965(8)
_cell_length_b                   8.3662(3)
_cell_length_c                   24.4494(12)
_cell_measurement_reflns_used    1833
_cell_measurement_temperature    290.04(10)
_cell_measurement_theta_max      24.5910
_cell_measurement_theta_min      4.1220
_cell_volume                     3318.2(3)
_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, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.04(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_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      0.00  98.00   1.00    8.00    --   25.05  57.00-180.00   98
  2  \w    -42.00  46.00   1.00    8.00    --   25.05 -57.00  30.00   88
  3  \w      6.00  60.00   1.00    8.00    --   25.05  77.00-120.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0065935000
_diffrn_orient_matrix_UB_12      -0.0225993000
_diffrn_orient_matrix_UB_13      -0.0293716000
_diffrn_orient_matrix_UB_21      -0.0215501000
_diffrn_orient_matrix_UB_22      -0.0690605000
_diffrn_orient_matrix_UB_23      0.0031334000
_diffrn_orient_matrix_UB_31      -0.0374723000
_diffrn_orient_matrix_UB_32      0.0436917000
_diffrn_orient_matrix_UB_33      -0.0102946000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            6101
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.50
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.265
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79197
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1424
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.186
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         3254
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0472
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0449P)^2^+0.6259P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1219
_reflns_number_gt                2199
_reflns_number_total             3254
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo8b02111_si_003.cif
_cod_data_source_block           majw_0327
_cod_original_cell_volume        3318.2(2)
_cod_database_code               4035770
_reflns_odcompleteness_completeness 99.67
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C12(H12)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C16(H16A,H16B,H16C)
;
_olex2_date_sample_data_collection 2018-03-28
_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 1.352
_oxdiff_exptl_absorpt_empirical_full_min 0.658