Organo-Catalyzed Regio- and Geometry-Specific Construction of β-Hydroxyl-α-vinyl Carboxylic Esters: Substrate Scope, Mechanistic Insights, and Applications.
Chai, Yonghai; Zhou, JinJin; Wu, Yanbin; Feng, Yingle; Wang, Panru; Chen, Yange; Wang, Xinying; Zhao, Beibei; Zhang, Qi; The Journal of organic chemistry 83 (2018) 10476–10486; doi:10.1021/acs.joc.8b01510

data_4035138
_publ_section_title
;
 Organo-Catalyzed Regio- and Geometry-Specific Construction of
 \b-Hydroxyl-\a-vinyl Carboxylic Esters: Substrate Scope, Mechanistic
 Insights, and Applications.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10476
_journal_page_last               10486
_journal_paper_doi               10.1021/acs.joc.8b01510
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C19 H19 Br O3'
_chemical_formula_sum            'C19 H19 Br O3'
_chemical_formula_weight         375.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-05-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.562(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.1424(4)
_cell_length_b                   5.80416(17)
_cell_length_c                   17.8991(4)
_cell_measurement_reflns_used    4895
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.3690
_cell_measurement_theta_min      6.3040
_cell_volume                     1723.70(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0356
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
  1 omega   19.00   57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000   60.0000 38

  2 omega  -22.00    9.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000   60.0000 31

  3 omega   13.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000  -30.0000 53

  4 omega   54.00   92.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397 -125.0000 -180.0000 38

  5 omega  -10.00   81.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397  -37.0000   60.0000 91

  6 omega   31.00  122.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397   37.0000 -120.0000 91

  7 omega   34.00   74.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397  -57.0000 -180.0000 40

  8 omega   51.00  101.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794 -111.0000 -120.0000 50

  9 omega   47.00   73.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -63.0000  120.0000 26

 10 omega   96.00  133.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -63.0000    0.0000 37

 11 omega   38.00   93.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -25.0000   90.0000 55

 12 omega   61.00   87.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -25.0000  120.0000 26

 13 omega   39.00   85.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -37.0000 -180.0000 46

 14 omega   50.00  141.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -77.0000 -120.0000 91

 15 omega   41.00  166.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794   12.0000  -60.0000 125

 16 omega  -70.00  -10.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  145.0000 -172.0000 60

 17 omega   -4.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000 -150.0000 46

 18 omega  -13.00   76.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397  -57.0000  -30.0000 89

 19 omega   25.00  126.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397   77.0000  -60.0000 101

 20 omega   34.00  124.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397   57.0000   30.0000 90

 21 omega   34.00  124.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -       55.5397   57.0000  120.0000 90

 22 omega   85.00  178.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794   37.0000   90.0000 93

 23 omega   41.00  110.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -77.0000   60.0000 69

 24 omega   81.00  178.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794   77.0000   30.0000 97

 25 omega   39.00  116.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794 -111.0000    0.0000 77

 26 omega   85.00  178.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794   37.0000    0.0000 93

 27 omega   85.00  178.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794   37.0000  150.0000 93

 28 omega   41.00  105.00   1.0000    2.9400
omega____ theta____ kappa____ phi______ frames
    -      111.0794  -50.0000  -30.0000 64
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0502729000
_diffrn_orient_matrix_UB_12      0.0163872000
_diffrn_orient_matrix_UB_13      -0.0842803000
_diffrn_orient_matrix_UB_21      -0.0780773000
_diffrn_orient_matrix_UB_22      -0.0114062000
_diffrn_orient_matrix_UB_23      0.0276670000
_diffrn_orient_matrix_UB_31      -0.0002936000
_diffrn_orient_matrix_UB_32      0.2645971000
_diffrn_orient_matrix_UB_33      0.0063954000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0260
_diffrn_reflns_av_unetI/netI     0.0193
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            13419
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.335
_diffrn_reflns_theta_min         5.106
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.349
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31926
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description
;
;
_exptl_crystal_F_000             768
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.673
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         3368
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0370
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0583P)^2^+0.6372P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2884
_reflns_number_total             3368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01510_si_003.cif
_cod_data_source_block           exp_11202
_cod_database_code               4035138
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'Br C O'
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C1(H1), C5(H5), C16(H16), C4(H4), C2(H2), C12(H12), C15(H15),
 C3(H3A), C13(H13)
2.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_olex2_submission_special_instructions 'No special instructions were received'