Enantioselective Copper-Catalyzed Formal [4 + 2] Cycloaddition of o-Aminophenol Derivatives with Propargylic Esters for Synthesis of Optically Active 3,4-Dihydro-2H-1,4-benzoxazines.
Liu, Zhen-Ting; Wang, Ya-Hui; Zhu, Fu-Lin; Hu, Xiang-Ping; Organic letters 18 (2016) 1190–; doi:10.1021/acs.orglett.6b00322

data_1542710
_publ_section_title
;
 Enantioselective Copper-Catalyzed Formal [4 + 2] Cycloaddition of
 o-Aminophenol Derivatives with Propargylic Esters for Synthesis of
 Optically Active 3,4-Dihydro-2H-1,4-benzoxazines.
;
_journal_issue                   5
_journal_name_full               'Organic letters'
_journal_page_first              1190
_journal_paper_doi               10.1021/acs.orglett.6b00322
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H18 Br N O'
_chemical_formula_sum            'C22 H18 Br N O'
_chemical_formula_weight         392.28
_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
_audit_creation_date             2016-01-08
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.08.17 svn.r3210 for OlexSys, GUI svn.r5083)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.7821(9)
_cell_length_b                   10.3912(9)
_cell_length_c                   35.968(3)
_cell_measurement_reflns_used    3689
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      19.899
_cell_measurement_theta_min      2.264
_cell_volume                     3656.1(6)
_computing_cell_refinement       'SAINT v6.02A (Bruker, 2001)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v6.02A (Bruker, 2001)'
_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    'Bruker SHELXTL'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0751
_diffrn_reflns_av_unetI/netI     0.1007
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            26135
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.384
_diffrn_reflns_theta_min         1.132
_exptl_absorpt_coefficient_mu    2.257
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5005
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.425
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 1453 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.019(7)
_refine_ls_extinction_coef       0.0011(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.922
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         9099
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.922
_refine_ls_R_factor_all          0.1165
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0278P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0815
_refine_ls_wR_factor_ref         0.0985
_reflns_Friedel_coverage         0.781
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                4631
_reflns_number_total             9099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00322_si_002.cif
_cod_data_source_block           cd15173
_cod_original_cell_volume        3656.0(6)
_cod_database_code               1542710
_shelx_estimated_absorpt_t_max   0.758
_shelx_estimated_absorpt_t_min   0.637
_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:
 C3(H3), C25(H25)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C38(H38A,H38B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C28(H28), C29(H29), C30(H30),
  C31(H31), C33(H33), C34(H34), C36(H36), C37(H37), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44)
2.d X=CH2 refined with riding coordinates:
 C2(H2A,H2B), C24(H24A,H24B)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'