Axially Chiral Enamides: Substituent Effects, Rotation Barriers, and Implications for their Cyclization Reactions.
Clark, Andrew J.; Curran, Dennis P.; Fox, David J.; Ghelfi, Franco; Guy, Collette S.; Hay, Benjamin; James, Natalie; Phillips, Jessica M.; Roncaglia, Fabrizio; Sellars, Philip B.; Wilson, Paul; Zhang, Hanmo; The Journal of organic chemistry 81 (2016) 5547–5565; doi:10.1021/acs.joc.6b00889

data_4036904
_publ_section_title
;
 Axially Chiral Enamides: Substituent Effects, Rotation Barriers, and
 Implications for their Cyclization Reactions.
;
_journal_issue                   13
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              5547
_journal_page_last               5565
_journal_paper_doi               10.1021/acs.joc.6b00889
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C19 H20 Br N O'
_chemical_formula_sum            'C19 H20 Br N O'
_chemical_formula_weight         358.27
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-04-21
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   15.6449(2)
_cell_length_b                   9.02047(12)
_cell_length_c                   23.2833(3)
_cell_measurement_reflns_used    13692
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.3078
_cell_measurement_theta_min      3.1311
_cell_volume                     3285.84(7)
_computing_cell_refinement
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_collection
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_data_reduction
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXH-1997 (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.954
_diffrn_measurement_details
;
  1 omega   46.00   95.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3155   77.0000  120.0000 49

  2 omega  -53.00   42.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3155  -38.0000 -150.0000 95

  3 omega    3.00   83.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3155   38.0000   30.0000 80

  4 omega    3.00   53.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3155   38.0000 -120.0000 50

  5 omega    4.00   29.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3155   38.0000  120.0000 25

  6 omega  -56.00   43.00   1.0000   50.0000
omega____ theta____ kappa____ phi______ frames
    -       16.3155  -38.0000   30.0000 99
;
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0106426000
_diffrn_orient_matrix_UB_12      -0.0583495000
_diffrn_orient_matrix_UB_13      0.0191197000
_diffrn_orient_matrix_UB_21      0.0432764000
_diffrn_orient_matrix_UB_22      -0.0042300000
_diffrn_orient_matrix_UB_23      0.0089442000
_diffrn_orient_matrix_UB_31      -0.0083477000
_diffrn_orient_matrix_UB_32      0.0525574000
_diffrn_orient_matrix_UB_33      0.0219561000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            35796
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         31.38
_diffrn_reflns_theta_min         3.14
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.504
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64682
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET)
(compiled Aug 27 2010,11:50:40)
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    1.448
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.481
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     202
_refine_ls_number_reflns         5161
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0464
_refine_ls_R_factor_gt           0.0336
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0337P)^2^+2.1190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0734
_refine_ls_wR_factor_ref         0.0780
_reflns_number_gt                4239
_reflns_number_total             5161
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo6b00889_si_002.cif
_cod_data_source_block           cg3
_cod_original_cell_volume        3285.85(7)
_cod_database_code               4036904
_chemical_oxdiff_formula         'C20 H20 N2 O2 Br'
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.98
_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:
 C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_res_checksum              19958