Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of Unsymmetrical α,ω-Diynes with Acenaphthylene.
Aida, Yukimasa; Shibata, Yu; Tanaka, Ken; The Journal of organic chemistry 83 (2018) 2617–2626; doi:10.1021/acs.joc.7b03042

data_4033486
_publ_section_title
;
 Rhodium-Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of Unsymmetrical
 \a,\w-Diynes with Acenaphthylene.
;
_journal_issue                   5
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2617
_journal_page_last               2626
_journal_paper_doi               10.1021/acs.joc.7b03042
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C41 H28 Br N O3, 0.5(C6 H14)'
_chemical_formula_sum            'C44 H35 Br N O3'
_chemical_formula_weight         705.64
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-11-30
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2016.03.30 svn.r3266 for Rigaku Oxford Diffraction, GUI svn.r5168)
;
_cell_angle_alpha                78.540(8)
_cell_angle_beta                 75.237(9)
_cell_angle_gamma                76.104(9)
_cell_formula_units_Z            2
_cell_length_a                   11.3679(13)
_cell_length_b                   11.7476(11)
_cell_length_c                   13.3386(13)
_cell_measurement_reflns_used    11402
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      23.4820
_cell_measurement_theta_min      2.3210
_cell_volume                     1654.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.12b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.12b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.12b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      193(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.955
_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    -28.00 110.00   0.50   70.00    --   20.00  54.00 118.24  276
  2  \w    -74.00 -16.00   0.50   70.00    --   20.00  54.00-103.21  116
  3  \w    -13.00  14.00   0.50   70.00    --   20.00  54.00-103.21   54
  4  \w     17.00  50.00   0.50   70.00    --   20.00  54.00-103.21   66
  5  \w     56.00 109.00   0.50   70.00    --   20.00  54.00-103.21  106
  6  \w    -72.00 -43.00   0.50   70.00    --   20.00  54.00  15.65   58
  7  \w    -37.00 -11.00   0.50   70.00    --   20.00  54.00  15.65   52
  8  \w     -4.00  62.00   0.50   70.00    --   20.00  54.00  15.65  132
  9  \w     69.00 110.00   0.50   70.00    --   20.00  54.00  15.65   82
 10  \w    -65.00 -39.00   0.50   70.00    --   20.00  54.00 -30.00   52
 11  \w    -22.00   4.00   0.50   70.00    --   20.00  54.00 -30.00   52
 12  \w     11.00  59.00   0.50   70.00    --   20.00  54.00 -30.00   96
 13  \w     75.00 110.00   0.50   70.00    --   20.00  54.00 -30.00   70
 14  \w    -70.00 110.00   0.50   70.00    --   20.00  54.00  60.00  360
 15  \w    -73.00 -38.00   0.50   70.00    --   20.00  54.00 150.00   70
 16  \w    -25.00  29.00   0.50   70.00    --   20.00  54.00 150.00  108
 17  \w     58.00 110.00   0.50   70.00    --   20.00  54.00 150.00  104
 18  \w    -63.00 -33.00   0.50   70.00    --   20.00  54.00  90.00   60
 19  \w    -16.00  11.00   0.50   70.00    --   20.00  54.00  90.00   54
 20  \w     85.00 110.00   0.50   70.00    --   20.00  54.00  90.00   50
 21  \w    -69.00 -39.00   0.50   70.00    --   20.00  54.00-150.00   60
 22  \w    -13.00  61.00   0.50   70.00    --   20.00  54.00-150.00  148
 23  \w     70.00 110.00   0.50   70.00    --   20.00  54.00-150.00   80
 24  \w    -45.00 -20.00   0.50   70.00    --   20.00  54.00-180.00   50
 25  \w     -7.00  43.00   0.50   70.00    --   20.00  54.00-180.00  100
 26  \w     82.00 109.00   0.50   70.00    --   20.00  54.00-180.00   54
 27  \w    -65.00   0.00   0.50   70.00    --   20.00  54.00 -60.00  130
 28  \w      6.00 110.00   0.50   70.00    --   20.00  54.00 -60.00  208
 29  \w    -68.00   7.00   0.50   70.00    --   20.00  54.00   0.00  150
 30  \w     40.00  75.00   0.50   70.00    --   20.00  54.00   0.00   70
 31  \w     85.00 110.00   0.50   70.00    --   20.00  54.00   0.00   50
 32  \w    -44.00 -19.00   0.50   70.00    --   20.00  54.00 -90.00   50
 33  \w      5.00  52.00   0.50   70.00    --   20.00  54.00 -90.00   94
 34  \w     85.00 110.00   0.50   70.00    --   20.00  54.00 -90.00   50
 35  \w    -68.00 -43.00   0.50   70.00    --   20.00  54.00 118.24   50
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0098901000
_diffrn_orient_matrix_UB_12      -0.0591796000
_diffrn_orient_matrix_UB_13      0.0260506000
_diffrn_orient_matrix_UB_21      0.0265884000
_diffrn_orient_matrix_UB_22      -0.0206145000
_diffrn_orient_matrix_UB_23      -0.0489207000
_diffrn_orient_matrix_UB_31      0.0594264000
_diffrn_orient_matrix_UB_32      0.0051297000
_diffrn_orient_matrix_UB_33      0.0042001000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1055
_diffrn_reflns_av_unetI/netI     0.1672
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            49261
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.669
_diffrn_reflns_theta_min         2.193
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.287
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87537
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.12b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.417
_exptl_crystal_description       block
_exptl_crystal_F_000             730
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.930
_refine_diff_density_min         -1.030
_refine_diff_density_rms         0.108
_refine_ls_abs_structure_details
;
 Flack x determined using 2876 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.994
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     859
_refine_ls_number_reflns         19003
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.994
_refine_ls_R_factor_all          0.1812
_refine_ls_R_factor_gt           0.0873
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1050P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1905
_refine_ls_wR_factor_ref         0.2422
_reflns_Friedel_coverage         0.942
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.899
_reflns_number_gt                9213
_reflns_number_total             19003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b03042_si_002.cif
_cod_data_source_block           (-)-5
_cod_depositor_comments          'Adding full bibliography for 4033486.cif.'
_cod_database_code               4033486
_chemical_oxdiff_formula         'C41 H28 Br1 N1 O3'
_chemical_oxdiff_usercomment     -80C
_reflns_odcompleteness_completeness 99.29
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.a Ternary CH refined with riding coordinates:
 C44(H44), C42(H42), C45(H45), C5(H5), C6(H6), C47(H47), C2(H2), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C85(H85A,H85B), C88(H88A,H88B), C87(H87A,H87B), C84(H84A,H84B)
2.c Aromatic/amide H refined with riding coordinates:
 C71(H71), C58(H58), C37(H37), C34(H34), C16(H16), C24(H24), C30(H30),
 C27(H27), C76(H76), C75(H75), C35(H35), C78(H78), C28(H28), C39(H39), C74(H74),
  C33(H33), C13(H13), C29(H29), C80(H80), C70(H70), C54(H54), C68(H68),
 C21(H21), C55(H55), C65(H65), C14(H14), C79(H79), C38(H38), C22(H22), C62(H62),
  C69(H69), C57(H57), C17(H17), C23(H23), C63A(H63A), C64A(H64A)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C48(H48A,H48B,H48C), C9(H9A,H9B,H9C), C50(H50A,H50B,H50C),
 C89(H89A,H89B,H89C), C83(H83A,H83B,H83C)
;
_shelx_shelxl_version_number     2016/6
_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 1.443
_oxdiff_exptl_absorpt_empirical_full_min 0.822