Enantioselective Alkynylation of Aromatic Aldehydes Catalyzed by a Sterically Highly Demanding Chiral-at-Rhodium Lewis Acid.
Luo, Shipeng; Zhang, Xiao; Zheng, Yu; Harms, Klaus; Zhang, Lilu; Meggers, Eric; The Journal of organic chemistry 82 (2017) 8995–9005; doi:10.1021/acs.joc.7b01394

data_4032695
_publ_section_title
;
 Enantioselective Alkynylation of Aromatic Aldehydes Catalyzed by a
 Sterically Highly Demanding Chiral-at-Rhodium Lewis Acid.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8995
_journal_page_last               9005
_journal_paper_doi               10.1021/acs.joc.7b01394
_journal_volume                  82
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C50 H50 N4 Rh S2, F6 P, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C50.5 H51 Cl F6 N4 P Rh S2'
_chemical_formula_weight         1061.40
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.3345(8)
_cell_length_b                   21.1548(12)
_cell_length_c                   34.813(2)
_cell_measurement_reflns_used    9997
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.9302
_cell_measurement_theta_min      2.3401
_cell_volume                     10556.8(10)
_computing_cell_refinement       'SAINT V8.37A (Bruker AXS Inc., 2015)'
_computing_data_collection       'APEX3 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V8.37A (Bruker AXS Inc., 2015)'
_computing_molecular_graphics    'DIAMOND (Crystal Impact)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'XT V2014/1 (Bruker AXS Inc., 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 7.9
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker D8 QUEST area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0876
_diffrn_reflns_av_unetI/netI     0.1133
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            72343
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.302
_diffrn_reflns_theta_min         2.253
_diffrn_source                   'microfocus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.541
_exptl_absorpt_correction_T_max  0.97
_exptl_absorpt_correction_T_min  0.70
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   ' '
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.336
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             4360
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.716
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
; 
 Flack x determined using 4724 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.034(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1312
_refine_ls_number_reflns         19079
_refine_ls_number_restraints     450
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1014
_refine_ls_R_factor_gt           0.0652
_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^)+(0.0575P)^2^+16.2367P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1376
_reflns_Friedel_coverage         0.835
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                14045
_reflns_number_total             19079
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b01394_si_002.cif
_cod_data_source_block           lspRhSAdam3_0m_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-Scan' changed to
'multi-scan' according to
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_cell_volume        10557.0(10)
_cod_original_formula_sum        'C50.50 H51 Cl F6 N4 P Rh S2'
_cod_database_code               4032695
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.737
_shelx_estimated_absorpt_t_max   0.973
_shelx_res_checksum              16941
_shelx_hkl_checksum              79890
_shelx_fab_checksum              65767