Rhodium-catalyzed atroposelective access to trisubstituted olefins <i>via</i> C-H bond olefination of diverse arenes.
Zhu, Xiaohan; Mi, Ruijie; Yin, Jie; Wang, Fen; Li, Xingwei; Chemical science 14 (2023) 7999–8005; doi:10.1039/d3sc02714g

data_1569430
_publ_section_title
;
 Rhodium-catalyzed atroposelective access to trisubstituted olefins
 <i>via</i> C-H bond olefination of diverse arenes.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              7999
_journal_page_last               8005
_journal_paper_doi               10.1039/d3sc02714g
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C55 H50 N2 O4 P Rh, 2(C H2 Cl2)'
_chemical_formula_sum            'C57 H54 Cl4 N2 O4 P Rh'
_chemical_formula_weight         1106.70
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-28 deposited with the CCDC.	2023-07-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.411(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.7897(15)
_cell_length_b                   13.9358(14)
_cell_length_c                   27.027(3)
_cell_measurement_reflns_used    9134
_cell_measurement_temperature    153.00
_cell_measurement_theta_max      68.412
_cell_measurement_theta_min      3.072
_cell_volume                     5418.5(10)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      153.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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  0.0533
_diffrn_reflns_av_unetI/netI     0.0503
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            74916
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.436
_diffrn_reflns_theta_min         3.072
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.010
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1148 before and 0.0939 after correction.
The Ratio of minimum to maximum transmission is 0.7732.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.357
_exptl_crystal_description       block
_exptl_crystal_F_000             2280
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.596
_refine_diff_density_min         -1.124
_refine_diff_density_rms         0.111
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.153(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1251
_refine_ls_number_reflns         19422
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0518
_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^)+(0.0511P)^2^+21.1435P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1319
_refine_ls_wR_factor_ref         0.1327
_reflns_Friedel_coverage         0.871
_reflns_Friedel_fraction_full    0.954
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                18977
_reflns_number_total             19422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02714g2.cif
_cod_data_source_block           s_CCDC2
_cod_depositor_comments
'Adding full bibliography for 1569428--1569430.cif.'
_cod_original_cell_volume        5418.6(9)
_cod_database_code               1569430
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.434
_shelx_estimated_absorpt_t_min   0.239
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.847(9)
 0.153(9)
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. Uiso/Uaniso restraints and constraints
C25 \\sim O7 \\sim C78: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
4. Others
 Fixed Y: Rh1(1.49525)
5.a Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C46(H46A,H46B), C54(H54A,H54B), C100(H10C,H10D), C106(H10E,
 H10F), C108(H10G,H10H), C17(H17A,H17B), C85(H85A,H85B), C43(H43A,H43B),
 C89(H89A,H89B), C13(H13A,H13B), C27(H27A,H27B), C109(H10A,H10B), C55(H55A,
 H55B), C7(H7A,H7B), C113(H11D,H11E)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C20(H20), C34(H34), C60(H60), C64(H64), C68(H68), C74(H74),
 C82(H82), C84(H84), C86(H86), C88(H88), C92(H92), C96(H96), C98(H98),
 C104(H104), C110(H110), C112(H112), C114(H114), C61(H61), C63(H63), C2(H2),
 C65(H65), C33(H33), C69(H69), C35(H35), C71(H71), C73(H73), C75(H75), C19(H19),
  C77(H77), C39(H39), C79(H79), C5(H5), C81(H81), C41(H41), C83(H83), C21(H21),
 C87(H87), C45(H45), C23(H23), C93(H93), C47(H47), C95(H95), C97(H97), C49(H49),
  C101(H101), C51(H51), C103(H103), C105(H105), C53(H53), C107(H107), C111(H111)
5.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C40(H40A,H40B,H40C), C48(H48A,H48B,H48C), C37(H37A,H37B,
 H37C), C11(H11A,H11B,H11C), C91(H91A,H91B,H91C), C99(H99A,H99B,H99C), C25(H25A,
 H25B,H25C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              46226
_shelx_fab_checksum              28703
_olex2_submission_special_instructions 'No special instructions were received'