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_4038761
_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         'C68 H58 N2 O8 Rh2'
_chemical_formula_sum            'C68 H58 N2 O8 Rh2'
_chemical_formula_weight         1236.981
_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_Int_Tables_number      4
_audit_creation_date             2020-05-05
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2020.04.27 svn.r7e0b91c7 for OlexSys, GUI svn.r6084)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.066(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.8716(8)
_cell_length_b                   18.221(3)
_cell_length_c                   18.301(2)
_cell_measurement_reflns_used    2289
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      62.7110
_cell_measurement_theta_min      2.5260
_cell_volume                     3291.2(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3-dev (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.8430
_diffrn_measured_fraction_theta_max 0.8430
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     97.00 167.00   0.50   25.00    --   87.02  89.00 154.00  140
  2  \w    115.00 147.00   0.50   25.00    --   87.02 125.00  90.00   64
  3  \w     10.00  46.00   0.50    5.00    --  -25.00  89.00 154.00   72
  4  \w     49.00  92.00   0.50   25.00    --   87.02 -89.00  38.00   86
  5  \w     85.00 121.00   0.50   25.00    --   87.02-125.00   0.00   72
  6  \w      6.00  32.00   0.50   10.00    --   15.00 -89.00  38.00   52
  7  \w     -2.00  45.00   0.50   10.00    --   15.00 -99.00 -30.00   94
  8  \w    -19.00   6.00   0.50   10.00    --  -15.00 -89.00  38.00   50
  9  \w    -87.00 -41.00   0.50   10.00    --  -15.00-178.00-120.00   92
 10  \w    -85.00  12.00   0.50   10.00    --  -15.00 -57.00  90.00  194
 11  \w    -36.00  -9.00   0.50   10.00    --  -15.00  89.00 154.00   54
 12  \w      6.00  31.00   0.50   10.00    --    6.62  89.00 154.00   50
 13  \w    -69.00 -42.00   0.50   25.00    --  -86.39  89.00 154.00   54
 14  \w    -94.00 -33.00   0.50   25.00    --  -86.39 125.00  60.00  122
 15  \w    -94.00 -11.00   0.50   25.00    --  -86.39 125.00-180.00  166
 16  \w   -161.00 -77.00   0.50   25.00    --  -86.39 -89.00  38.00  168
 17  \w   -155.00-152.00   0.50   25.00    --  -86.39 -95.00 -60.00    6
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1352508000
_diffrn_orient_matrix_UB_12      0.0090888000
_diffrn_orient_matrix_UB_13      0.0425161000
_diffrn_orient_matrix_UB_21      0.0450713000
_diffrn_orient_matrix_UB_22      -0.0763753000
_diffrn_orient_matrix_UB_23      -0.0262675000
_diffrn_orient_matrix_UB_31      0.0637637000
_diffrn_orient_matrix_UB_32      0.0348864000
_diffrn_orient_matrix_UB_33      -0.0678163000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0761
_diffrn_reflns_av_unetI/netI     0.1376
_diffrn_reflns_Laue_measured_fraction_full 0.8430
_diffrn_reflns_Laue_measured_fraction_max 0.8430
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            9572
_diffrn_reflns_point_group_measured_fraction_full 0.6381
_diffrn_reflns_point_group_measured_fraction_max 0.6381
_diffrn_reflns_theta_full        57.8985
_diffrn_reflns_theta_max         57.90
_diffrn_reflns_theta_min         3.42
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.468
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70303
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       needle
_exptl_crystal_F_000             1272.266
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.112
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.052
_refine_diff_density_max         0.8981
_refine_diff_density_min         -0.8021
_refine_diff_density_rms         0.1212
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.08(3)
_refine_ls_d_res_high            0.9101
_refine_ls_d_res_low             12.9111
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0319
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    108
_refine_ls_number_parameters     784
_refine_ls_number_reflns         5823
_refine_ls_number_restraints     1007
_refine_ls_restrained_S_all      0.9422
_refine_ls_R_factor_all          0.1024
_refine_ls_R_factor_gt           0.0689
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1198P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1717
_refine_ls_wR_factor_ref         0.1890
_reflns_Friedel_coverage         0.417
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              17
_reflns_limit_k_min              -16
_reflns_limit_l_max              20
_reflns_limit_l_min              -20
_reflns_number_gt                4013
_reflns_number_total             5823
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo0c01276_si_005.cif
_cod_data_source_block           BDW-3-30-2_4
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_original_formula_sum        C68H58N2O8Rh2
_cod_database_code               4038761
_chemical_oxdiff_formula         C68H58N2O8Rh2
_reflns_odcompleteness_completeness 83.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     58.86
_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 planarity
 C11, C13, C14, C15, C16
 with sigma of 0.002
 C5B, C6B, C7B, C8B, C9B, C10B
 with sigma of 0.002
 C5, C6, C7, C8, C9, C10
 with sigma of 0.002
 C3D, C5D, C6D, C7D, C8D, C9D, C10D
 with sigma of 0.002
 C3C, C5C, C6C, C7C, C8C, C9C, C10C
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(C1D) \\sim Ueq, Uanis(C2D) \\sim Ueq, Uanis(O1D) \\sim Ueq, Uanis(O2D)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C12D) \\sim Ueq, Uanis(C13D) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(O1B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C67) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C70) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(N2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O2C) \\sim Ueq, Uanis(C1C) \\sim Ueq, Uanis(O1C) \\sim Ueq: with sigma of
0.002 and sigma for terminal atoms of 0.004
Uanis(C6C) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(N1) \\sim Ueq, Uanis(C68) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C69) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(Rh1) \\sim Ueq, Uanis(Rh2) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 O1D, O2D, C1D, C2D, C3D, C4D, C5D, C6D, C7D, C8D, C9D, C10D, C11D, C12D, C13D,
  C14D, C15D, C16D
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1B, O2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B,
  C14B, C15B, C16B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N1, C67, C68
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2, C69, C70
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1C, O2C, C1C, C2C, C3C, C4C, C5C, C6C, C7C, C8C, C9C, C10C, C11C, C12C, C13C,
  C14C, C15C, C16C
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{O1B, O2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B,
C14B, C15B, C16B} sigma for 1-2: 0.002, 1-3: 0.002
as in
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16}
{O1B, O2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B,
C14B, C15B, C16B} sigma for 1-2: 0.002, 1-3: 0.002
as in
{O1C, O2C, C1C, C2C, C3C, C4C, C5C, C6C, C7C, C8C, C9C, C10C, C11C, C12C, C13C,
C14C, C15C, C16C}
{O1B, O2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B,
C14B, C15B, C16B} sigma for 1-2: 0.002, 1-3: 0.002
as in
{O1D, O2D, C1D, C2D, C3D, C4D, C5D, C6D, C7D, C8D, C9D, C10D, C11D, C12D, C13D,
C14D, C15D, C16D}
6.a Ternary CH refined with riding coordinates:
 C3(H3), C3B(H3B), C3C(H3C), C3D(H3D), C68(H68a), C70(H70a)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4a,H4b), C4B(H4Ba,H4Bb), C4C(H4Ca,H4Cb), C4D(H4Da,H4Db)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C6B(H6B), C7B(H7B), C8B(H8B), C9B(H9B), C10B(H10B),
 C12B(H12B), C13B(H13B), C14B(H14B), C15B(H15B), C16B(H16B), C6C(H6C), C7C(H7C),
  C8C(H8C), C9C(H9C), C10C(H10C), C12C(H12C), C13C(H13C), C14C(H14C),
 C15C(H15C), C16C(H16C), C6D(H6D), C7D(H7D), C8D(H8D), C9D(H9D), C10D(H10D),
 C12D(H12D), C13D(H13D), C14D(H14D), C15D(H15D), C16D(H16D)
;
_smtbx_masks_void_probe_radius   0.6
_smtbx_masks_void_truncation_radius 1.2
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone'
_olex2_submission_original_sample_id BDW-3-30-2
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.349
_oxdiff_exptl_absorpt_empirical_full_min 0.190