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_4125615
_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         'C46 H24 Cl2 F24 Rh2'
_chemical_formula_sum            'C46 H24 Cl2 F24 Rh2'
_chemical_formula_weight         1309.37
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-05-09
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.8348(6)
_cell_length_b                   21.7778(10)
_cell_length_c                   30.4291(13)
_cell_measurement_reflns_used    9392
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.10
_cell_measurement_theta_min      3.54
_cell_volume                     9830.7(7)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0748
_diffrn_reflns_av_unetI/netI     0.0682
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            84113
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.186
_diffrn_reflns_theta_min         3.544
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.583
_exptl_absorpt_correction_T_max  0.5154
_exptl_absorpt_correction_T_min  0.2873
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1057 before and 0.0883 after correction.
The Ratio of minimum to maximum transmission is 0.5574.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.769
_exptl_crystal_description       block
_exptl_crystal_F_000             5120
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.124
_refine_diff_density_max         2.016
_refine_diff_density_min         -0.822
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
 Flack x determined using 7165 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1417
_refine_ls_number_reflns         18555
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0486
_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^)+(0.0812P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1183
_refine_ls_wR_factor_ref         0.1215
_reflns_Friedel_coverage         0.830
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                17160
_reflns_number_total             18555
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b00943_si_002.cif
_cod_data_source_block           x1604008
_cod_database_code               4125615
_shelx_estimated_absorpt_t_max   0.453
_shelx_estimated_absorpt_t_min   0.237
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F68A-C82
 1.35 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F72, F72A, F73, F73A, F74A, F74, C96
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F19, F19A, F20A, F20, F21, F21A, C45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F66, F66A, F67, F67A, F68, F68A, C82
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F72A)=Sof(F73A)=Sof(F74A)=1-FVAR(1)
 Sof(F72)=Sof(F73)=Sof(F74)=FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(2)
 Sof(F66A)=Sof(F67A)=Sof(F68A)=1-FVAR(3)
 Sof(F66)=Sof(F67)=Sof(F68)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C11(H11), C13(H13), C15(H15), C33(H33), C34(H34), C36(H36), C37(H37),
 C51(H51), C61(H61), C62(H62), C64(H64), C83(H83), C84(H84), C86(H86), C87(H87)
5.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C35(H35A,H35B), C63(H63A,H63B), C85(H85A,H85B)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C8(H8), C17(H17), C19(H19), C21(H21), C26(H26), C28(H28),
 C30(H30), C40(H40), C42(H42), C44(H44), C54(H54), C56(H56), C58(H58), C67(H67),
  C69(H69), C71(H71), C76(H76), C78(H78), C80(H80), C90(H90), C92(H92), C94(H94)
;
_shelx_res_checksum              42515
_shelx_hkl_checksum              41080
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-04-26
_olex2_date_sample_submission    2016-04-26
_olex2_submission_original_sample_id SLB_EQ_8054_R
_olex2_submission_special_instructions 'No special instructions were received'