Comparison of 1,2-Diarylcyclopropanecarboxylates with 1,2,2-Triarylcyclopropanecarboxylates as Chiral Ligands for Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.
Wertz, Benjamin; Ren, Zhi; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01276

data_4038758
_publ_section_title
;
 Comparison of 1,2-Diarylcyclopropanecarboxylates with
 1,2,2-Triarylcyclopropanecarboxylates as Chiral Ligands for
 Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01276
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C64 H52 O8 Rh2, 2(C7 H8)'
_chemical_formula_sum            'C78 H68 O8 Rh2'
_chemical_formula_weight         1339.14
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2016-09-01
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2016.08.25 svn.r3337 for OlexSys, GUI svn.r5221)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   31.5424(7)
_cell_length_b                   8.3838(2)
_cell_length_c                   11.9960(3)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.43
_cell_measurement_theta_min      3.68
_cell_volume                     3172.28(13)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.11 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2014/4 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'd8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0640
_diffrn_reflns_av_unetI/netI     0.0619
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            21186
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.500
_diffrn_reflns_theta_min         2.802
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           35
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.671
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_description       prism
_exptl_crystal_F_000             1380
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.860
_refine_diff_density_min         -0.544
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 2256 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         6408
_refine_ls_number_restraints     296
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0389
_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^)+3.5901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0802
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    0.981
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                5736
_reflns_number_total             6408
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01276_si_002.cif
_cod_data_source_block           bdw-unknown
_cod_database_code               4038758
_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
2. Restrained distances
 C8S-C9S
 1.506 with sigma of 0.02
 C8S-C14S
 2.525 with sigma of 0.04
 C8S-C10S
 2.524 with sigma of 0.04
 C9S-C14S
 1.392 with sigma of 0.02
 C9S-C13S
 2.418 with sigma of 0.04
 C9S-C10S
 1.395 with sigma of 0.02
 C9S-C11S
 2.412 with sigma of 0.04
 C14S-C13S
 1.378 with sigma of 0.02
 C14S-C12S
 2.391 with sigma of 0.04
 C13S-C12S
 1.39 with sigma of 0.02
 C13S-C11S
 2.396 with sigma of 0.04
 C12S-C11S
 1.381 with sigma of 0.02
 C12S-C10S
 2.397 with sigma of 0.04
 C11S-C10S
 1.38 with sigma of 0.02
 C1S'-C2S'
 1.51 with sigma of 0.02
 C2S'-C7S' \\sim C7S'-C6S' \\sim C6S'-C5S' \\sim C5S'-C4S' \\sim C4S'-C3S'
\\sim C3S'-C2S'
 with sigma of 0.02
 C2S'-C4S' \\sim C2S'-C6S' \\sim C3S'-C5S' \\sim C7S'-C3S' \\sim C6S'-C4S'
\\sim C7S'-C5S'
 with sigma of 0.04
 C1S'-C3S' \\sim C1S'-C7S'
 with sigma of 0.04
3. Restrained planarity
 C1S', C2S', C7S', C6S', C5S', C4S', C3S'
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1S' \\sim C2S' \\sim C7S' \\sim C6S' \\sim C5S' \\sim C4S' \\sim C3S': within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C31) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C9S) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C6S') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C5S') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C6S') = Uanis(C4S')
Uanis(C1S) = Uanis(C2S) = Uanis(C7S) = Uanis(C6S) = Uanis(C5S) = Uanis(C4S) =
Uanis(C3S)
Uanis(C7S') = Uanis(C7S)
Uanis(C2S) = Uanis(C2S')
Uanis(C3S) = Uanis(C3S')
Uanis(C1S) = Uanis(C1S')
5. Rigid body (RIGU) restrains
 C1S', C2S', C7S', C6S', C5S', C4S', C3S'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C18, C28, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C9S, C8S, C14S, C10S, C13S, C11S, C12S
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C2S, C1S', C2S', C7S', C3S', C6S', C4S', C7S, C4S, C3S, C5S', C1S, C6S, C5S
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: C9S(0.5) C11S(0.5) H11S(0.5) C13S(0.5) H13S(0.5) C8S(0.5)
 H8SA(0.5) H8SB(0.5) H8SC(0.5) C14S(0.5) H14S(0.5) C12S(0.5) H12S(0.5)
 C10S(0.5) H10S(0.5) C1S'(0.25) H1SA(0.25) H1SB(0.25) H1SC(0.25) C2S'(0.25)
 C7S'(0.25) H7S'(0.25) C6S'(0.25) H6S'(0.25) C5S'(0.25) H5S'(0.25) C4S'(0.25)
 H4S'(0.25) C3S'(0.25) H3S'(0.25) C1S(0.25) H1SD(0.25) H1SE(0.25) H1SF(0.25)
 C2S(0.25) C7S(0.25) H7S(0.25) C6S(0.25) H6S(0.25) C5S(0.25) H5S(0.25)
 C4S(0.25) H4S(0.25) C3S(0.25) H3S(0.25)
7.a Free rotating group:
 C1S(C2S,C7S,C6S,C5S,C4S,C3S)
7.b Ternary CH refined with riding coordinates:
 C3(H3), C19(H19)
7.c Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C20(H20A,H20B)
7.d Aromatic/amide H refined with riding coordinates:
 C25(H25), C29(H29), C11S(H11S), C7(H7), C31(H31), C8(H8), C9(H9), C6(H6),
 C13S(H13S), C24(H24), C12(H12), C26(H26), C13(H13), C28(H28), C14(H14),
 C30(H30), C15(H15), C32(H32), C16(H16), C10(H10), C14S(H14S), C12S(H12S),
 C22(H22), C10S(H10S), C23(H23), C7S'(H7S'), C6S'(H6S'), C5S'(H5S'), C4S'(H4S'),
  C3S'(H3S'), C7S(H7S), C6S(H6S), C5S(H5S), C4S(H4S), C3S(H3S)
7.e Idealised Me refined as rotating group:
 C8S(H8SA,H8SB,H8SC), C1S'(H1SA,H1SB,H1SC), C1S(H1SD,H1SE,H1SF)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id BDW-unknown
_olex2_submission_special_instructions 'No special instructions were received'