Synthesis of Complex Tertiary Glycolates by Enantioconvergent Arylation of Stereochemically Labile α-Keto Esters.
Bartlett, Samuel L.; Keiter, Kimberly M.; Johnson, Jeffrey S.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b00943

data_4125614
_publ_section_title
;
 Synthesis of Complex Tertiary Glycolates by Enantioconvergent Arylation
 of Stereochemically Labile \a-Keto Esters.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b00943
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H21 Br O3'
_chemical_formula_sum            'C22 H21 Br O3'
_chemical_formula_weight         413.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-04-22
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.7261(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.8041(3)
_cell_length_b                   5.9064(2)
_cell_length_c                   19.9549(8)
_cell_measurement_reflns_used    9735
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.50
_cell_measurement_theta_min      4.45
_cell_volume                     916.68(6)
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            14210
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        66.561
_diffrn_reflns_theta_max         66.561
_diffrn_reflns_theta_min         2.222
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.208
_exptl_absorpt_correction_T_max  0.9431
_exptl_absorpt_correction_T_min  0.5141
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0748 before and 0.0541 after correction.
The Ratio of minimum to maximum transmission is 0.5451.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       needle
_exptl_crystal_F_000             424
_exptl_crystal_size_max          0.515
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.317
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.020(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     242
_refine_ls_number_reflns         3138
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0233
_refine_ls_R_factor_gt           0.0223
_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^)+(0.0317P)^2^+0.0942P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0537
_refine_ls_wR_factor_ref         0.0541
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                3042
_reflns_number_total             3138
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00943_si_001.cif
_cod_data_source_block           x1604006
_cod_database_code               4125614
_shelx_estimated_absorpt_t_max   0.877
_shelx_estimated_absorpt_t_min   0.289
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.980(18) 0.020(18)
2. 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
3.a Ternary CH refined with riding coordinates:
 C8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C18(H18), C19(H19), C21(H21), C22(H22),
 C23(H23), C24(H24), C26(H26)
3.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              87539
_shelx_hkl_checksum              542
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-04-20
_olex2_date_sample_submission    2016-04-20
_olex2_submission_original_sample_id 'SLB 8060 2'
_olex2_submission_special_instructions 'No special instructions were received'