Enantioselective Iron-Catalyzed Cross-[4+4]-Cycloaddition of 1,3-Dienes Provides Chiral Cyclooctadienes.
Braconi, Elena; Götzinger, Alissa C; Cramer, Nicolai; Journal of the American Chemical Society 142 (2020) 19819–19824; doi:10.1021/jacs.0c09486

data_4135358
_publ_section_title
;
 Enantioselective Iron-Catalyzed Cross-[4+4]-Cycloaddition of 1,3-Dienes
 Provides Chiral Cyclooctadienes.
;
_journal_issue                   47
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              19819
_journal_page_last               19824
_journal_paper_doi               10.1021/jacs.0c09486
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C46 H52 Cl2 Rh2'
_chemical_formula_sum            'C46 H52 Cl2 Rh2'
_chemical_formula_weight         881.59
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.5785(5)
_cell_length_b                   11.9443(4)
_cell_length_c                   10.9829(5)
_cell_measurement_reflns_used    10177
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      32.7160
_cell_measurement_theta_min      3.2900
_cell_volume                     1912.45(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.951
_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    -34.00  11.00   1.00   14.69    --  -17.55  77.00   0.00   45
  2  \w    -23.00  61.00   1.00   14.69    --  -17.55  19.00 120.00   84
  3  \w   -102.00 -68.00   1.00   14.69    --  -17.55 178.00 -30.00   34
  4  \w    -54.00   8.00   1.00   14.69    --  -17.55 -57.00 -90.00   62
  5  \w    -42.00   0.00   1.00   14.69    --  -17.55 -77.00 120.00   42
  6  \w    -50.00  61.00   1.00   14.69    --  -17.55  19.00 -90.00  111
  7  \w     25.00  70.00   1.00   14.69    --   18.17  57.00 150.00   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0112088000
_diffrn_orient_matrix_UB_12      0.0019374000
_diffrn_orient_matrix_UB_13      -0.0628366000
_diffrn_orient_matrix_UB_21      0.0421592000
_diffrn_orient_matrix_UB_22      -0.0265161000
_diffrn_orient_matrix_UB_23      -0.0142450000
_diffrn_orient_matrix_UB_31      -0.0214664000
_diffrn_orient_matrix_UB_32      -0.0531152000
_diffrn_orient_matrix_UB_33      0.0048378000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            25992
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.940
_diffrn_reflns_theta_min         2.881
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.035
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.675
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear intense yellow'
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_description       prism
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.438
_exptl_crystal_size_mid          0.196
_exptl_crystal_size_min          0.169
_refine_diff_density_max         0.402
_refine_diff_density_min         -0.705
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         6660
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0343
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0220P)^2^+0.1732P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0504
_refine_ls_wR_factor_ref         0.0536
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                6071
_reflns_number_total             6660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09486_si_004.cif
_cod_data_source_block           ebr-03-159
_cod_depositor_comments
'Adding full bibliography for 4135355--4135358.cif.'
_cod_original_cell_volume        1912.46(13)
_cod_database_code               4135358
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C46 H52 Cl2 Rh2'
_shelx_estimated_absorpt_t_max   0.844
_shelx_estimated_absorpt_t_min   0.660
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.97(3)
 0.03(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C2(H2), C5(H5), C6(H6), C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C8(H8A,H8B), C9(H9A,H9B), C16(H16A,H16B), C17(H17A,
 H17B)
3.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C19(H19), C20(H20),
 C21(H21), C22(H22), C23(H23)
;
_shelx_res_checksum              57452
_shelx_hkl_checksum              58472
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.329
_oxdiff_exptl_absorpt_empirical_full_min 0.781