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_4036905
_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         'C21 H24 Br N O'
_chemical_formula_sum            'C21 H24 Br N O'
_chemical_formula_weight         386.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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                90.048(2)
_cell_angle_beta                 96.165(2)
_cell_angle_gamma                112.241(3)
_cell_formula_units_Z            2
_cell_length_a                   7.9989(2)
_cell_length_b                   9.6732(2)
_cell_length_c                   13.3484(3)
_cell_measurement_reflns_used    12356
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      70.5357
_cell_measurement_theta_min      4.9404
_cell_volume                     949.49(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -41.00  -12.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6947  -57.0000   90.0000 29

  2 omega -114.00  -47.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6947  -57.0000   90.0000 67

  3 omega  -80.00  -12.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6947  -57.0000  -90.0000 68

  4 omega  -74.00   29.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6947   77.0000   90.0000 103

  5 omega  -50.00   35.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6947   38.0000 -120.0000 85

  6 omega   23.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6947 -125.0000   30.0000 68

  7 omega   13.00   44.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6947   57.0000  150.0000 31

  8 omega   10.00   36.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   89.0000 -161.0000 26

  9 omega    8.00   33.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   90.0000  -31.0000 25

 10 omega    8.00   33.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       46.0000   90.0000   93.0000 25

 11 omega  -47.00  -22.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.5000  -77.0000    0.0000 25

 12 omega   96.00  136.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  112.0000 40

 13 omega   24.00   59.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   78.0000  142.0000 35

 14 omega   25.00  105.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   79.0000 -172.0000 80

 15 omega   27.00   53.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       58.0000   77.0000  112.0000 26

 16 omega   28.00   55.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       62.0000   77.0000 -111.0000 27

 17 omega  114.00  139.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000   21.0000 25

 18 omega   32.00   87.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000  -27.0000 55

 19 omega   33.00   58.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       66.0000   77.0000   21.0000 25

 20 omega   36.00   65.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   79.0000   61.0000 29

 21 omega   36.00   64.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   78.0000  -74.0000 28

 22 omega  113.00  144.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       70.0000   79.0000   61.0000 31

 23 omega   40.00   70.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       74.0000   78.0000 -119.0000 30

 24 omega   23.00   49.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -94.0000 -180.0000 26

 25 omega   41.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -94.0000    0.0000 68

 26 omega  121.00  147.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   61.0000  120.0000 26

 27 omega   66.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  120.0000 44

 28 omega  134.00  160.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  120.0000 26

 29 omega  115.00  141.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000 -150.0000 26

 30 omega   71.00  173.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   61.0000  150.0000 102

 31 omega   66.00  170.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000   90.0000 104

 32 omega   81.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000  -90.0000 31

 33 omega   61.00  135.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  179.0000   60.0000 74

 34 omega   66.00  101.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000   30.0000 35

 35 omega  141.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -120.0000 36

 36 omega  142.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  111.0000 -150.0000 36

 37 omega   66.00   91.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -120.0000 25

 38 omega  133.00  158.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  150.0000 25

 39 omega   69.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -45.0000 -150.0000 29

 40 omega   66.00  101.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  150.0000 35

 41 omega   27.00   64.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -45.0000 -150.0000 37

 42 omega   39.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -94.0000  150.0000 67

 43 omega   84.00  113.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000 -111.0000   90.0000 29

 44 omega   66.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  -60.0000 44

 45 omega  134.00  159.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  -60.0000 25

 46 omega  100.00  139.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  111.0000 -150.0000 39

 47 omega   69.00   95.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -150.0000 26

 48 omega   84.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -94.0000 -120.0000 25

 49 omega   24.00   74.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000 -111.0000   90.0000 50

 50 omega  108.00  139.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000   30.0000 31

 51 omega   23.00   53.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -94.0000 -120.0000 30

 52 omega  135.00  168.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000   60.0000 33

 53 omega  121.00  165.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000  -90.0000 44

 54 omega   74.00  102.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   61.0000  120.0000 28

 55 omega   68.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000   60.0000 47

 56 omega   56.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  179.0000  -90.0000 59

 57 omega   42.00  120.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000 -161.0000 -153.0000 78

 58 omega   74.00  110.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000 -150.0000 36

 59 omega   67.00  130.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  -90.0000 63

 60 omega  147.00  174.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  111.0000   30.0000 27

 61 omega  108.00  133.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -180.0000 25

 62 omega   69.00  127.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  -30.0000 58

 63 omega   73.00  121.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000  -30.0000 48

 64 omega   68.00   94.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000 -180.0000 26

 65 omega  100.00  131.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  111.0000   30.0000 31

 66 omega   70.00  116.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  179.0000  120.0000 46

 67 omega   68.00  142.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000    0.0000 74

 68 omega  126.00  152.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000  -30.0000 26

 69 omega  114.00  139.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000   90.0000 25

 70 omega   72.00  118.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -61.0000  150.0000 46

 71 omega  153.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   77.0000  -30.0000 25

 72 omega   77.00  122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000 -120.0000 45

 73 omega   98.00  135.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000   45.0000   30.0000 37

 74 omega   66.00  107.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      100.0000  -94.0000 -180.0000 41
;
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0150453000
_diffrn_orient_matrix_UB_12      -0.1081570000
_diffrn_orient_matrix_UB_13      0.0863247000
_diffrn_orient_matrix_UB_21      -0.0947332000
_diffrn_orient_matrix_UB_22      -0.1340076000
_diffrn_orient_matrix_UB_23      -0.0760205000
_diffrn_orient_matrix_UB_31      0.1862541000
_diffrn_orient_matrix_UB_32      -0.0031212000
_diffrn_orient_matrix_UB_33      -0.0164828000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0894
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            17863
_diffrn_reflns_theta_full        70.67
_diffrn_reflns_theta_max         70.67
_diffrn_reflns_theta_min         4.94
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.987
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21873
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
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    1.351
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             400
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.504
_refine_diff_density_min         -0.377
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     221
_refine_ls_number_reflns         3631
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0376
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0519P)^2^+0.3471P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0947
_refine_ls_wR_factor_ref         0.0952
_reflns_number_gt                3567
_reflns_number_total             3631
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo6b00889_si_002.cif
_cod_data_source_block           cg4
_cod_database_code               4036905
_chemical_oxdiff_formula         'C20 H20 N2 O2 Br'
_reflns_odcompleteness_completeness 96.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_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:
 C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C18(H18), C19(H19), C20(H20),
 C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C3(H3A,H3B,H3C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_shelx_res_checksum              15578