Palladium-catalyzed highly regioselective 6-exo-dig cyclization and alkenylation of ortho-ethynylanilides: the synthesis of polyene-substituted benzo[d][1,3]oxazines
Zhong-Jian Cai; Chao Yang; Shun-Yi Wang; Shun-Jun Ji; Chem.Commun. 51 (2015) 14267–; doi:10.1039/C5cc06510K

data_7117761
_publ_section_title
;
 Palladium-catalyzed highly regioselective 6-exo-dig cyclization and
 alkenylation of ortho-ethynylanilides: the synthesis of
 polyene-substituted benzo[d][1,3]oxazines
;
_journal_name_full               Chem.Commun.
_journal_page_first              14267
_journal_paper_doi               10.1039/C5cc06510K
_journal_volume                  51
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C25 H19 N O3'
_chemical_formula_sum            'C25 H19 N O3'
_chemical_formula_weight         381.41
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-04-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-04-27 deposited with the CCDC.
2015-08-25 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   4.11501(15)
_cell_length_b                   10.0552(3)
_cell_length_c                   45.8911(16)
_cell_measurement_reflns_used    3347
_cell_measurement_temperature    223.01(10)
_cell_measurement_theta_max      73.2260
_cell_measurement_theta_min      3.8490
_cell_volume                     1898.85(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      223.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4471
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega  -38.00   22.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.2343   37.0000   90.0000 60

  2 omega -110.00  -58.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.2343 -150.0000  137.0000 52

  3 omega -116.00  -14.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.2343  -37.0000  120.0000 102

  4 omega   31.00   73.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.2343 -125.0000  -30.0000 42

  5 omega   40.00   77.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -45.0000   60.0000 37

  6 omega   95.00  177.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   45.0000  -30.0000 82

  7 omega   35.00   83.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000    0.0000 48

  8 omega   28.00   85.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -30.0000  150.0000 57

  9 omega  112.00  138.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   45.0000 -120.0000 26

 10 omega  152.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522   45.0000 -120.0000 26

 11 omega   32.00  136.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522  -61.0000 -180.0000 104

 12 omega   28.00  110.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      105.9522 -111.0000   30.0000 82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.3486298000
_diffrn_orient_matrix_UB_12      -0.0539663000
_diffrn_orient_matrix_UB_13      -0.0030779000
_diffrn_orient_matrix_UB_21      0.1314516000
_diffrn_orient_matrix_UB_22      -0.1224637000
_diffrn_orient_matrix_UB_23      -0.0163561000
_diffrn_orient_matrix_UB_31      0.0368647000
_diffrn_orient_matrix_UB_32      -0.0744656000
_diffrn_orient_matrix_UB_33      0.0291659000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0314
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       56
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            8049
_diffrn_reflns_theta_full        73.37
_diffrn_reflns_theta_max         73.37
_diffrn_reflns_theta_min         3.85
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.705
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35974
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.188
_refine_diff_density_min         -0.207
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.2(3)
_refine_ls_extinction_coef       0.0035(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.907
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3585
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.907
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0405
_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^)+(0.1000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1147
_refine_ls_wR_factor_ref         0.1237
_reflns_number_gt                3204
_reflns_number_total             3585
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5cc06510k2.cif
_cod_data_source_block           g150425c
_cod_database_code               7117761
_chemical_oxdiff_formula         C11H11N11O11
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
2.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_olex2_date_sample_data_collection 2015-04-25
_olex2_submission_special_instructions 'No special instructions were received'