Nickel-Catalyzed Skeletal Transformation of Tropone Derivatives via C–C Bond Activation: Catalyst-Controlled Access to Diverse Ring Systems
Kodama, Takuya; Saito, Kanako; Tobisu, Mamoru; Chemical Science  (2022) –; doi:10.1039/D2SC01394K

data_1566745
_publ_section_title
;
 Nickel-Catalyzed Skeletal Transformation of Tropone Derivatives via C--C
 Bond Activation: Catalyst-Controlled Access to Diverse Ring Systems
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01394K
_journal_year                    2022
_chemical_formula_moiety         'C69 H76 Ni O P2, C4 H7 O, C4 H6 O'
_chemical_formula_sum            'C77 H89 Ni O3 P2'
_chemical_formula_weight         1183.13
_chemical_properties_physical    Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-10-14 deposited with the CCDC.	2022-04-04 downloaded from the CCDC.
;
_cell_angle_alpha                104.7600(10)
_cell_angle_beta                 97.2130(10)
_cell_angle_gamma                100.5840(10)
_cell_formula_units_Z            2
_cell_length_a                   10.9952(2)
_cell_length_b                   14.1370(2)
_cell_length_c                   21.6909(3)
_cell_measurement_reflns_used    19254
_cell_measurement_temperature    123
_cell_measurement_theta_max      76.3900
_cell_measurement_theta_min      3.3660
_cell_volume                     3151.76(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.43a (Rigaku OD, 2019)'
_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_temperature      123
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.959
_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     25.00 120.00   0.50    0.05    --   47.45  77.00 150.00  190
  2  \w    117.00 142.00   0.50    0.11    --   70.50  77.00  90.00   50
  3  \w     90.00 120.00   0.50    0.05    --   47.45 125.00   0.00   60
  4  \w     72.00  97.00   0.50    0.11    --   70.50 155.00 -69.00   50
  5  \w     61.00  86.00   0.50    0.05    --   47.45 155.00 -69.00   50
  6  \w     61.00 112.00   0.50    0.11    --   70.50  77.00  90.00  102
  7  \w     76.00 119.00   0.50    0.05    --   47.45 119.00 133.00   86
  8  \w     25.00  50.00   0.50    0.05    --   47.45-119.00  48.00   50
  9  \w     35.00  60.00   0.50    0.11    --   70.50-119.00  48.00   50
 10  \w     45.00  70.00   0.50    0.05    --   47.45-155.00-108.00   50
 11  \w     49.00 137.00   0.50    0.11    --   70.50-155.00-108.00  176
 12  \w    -62.00 -34.00   0.50    0.11    -- -106.00  37.00  90.00   56
 13  \w    -87.00 -33.00   0.50    0.05    --  -47.45 119.00 133.00  108
 14  \w   -112.00 -63.00   0.50    0.11    -- -106.00 119.00 133.00   98
 15  \w   -117.00 -33.00   0.50    0.11    -- -106.00 125.00 150.00  168
 16  \w   -121.00 -33.00   0.50    0.11    -- -106.00  57.00 150.00  176
 17  \w   -119.00 -72.00   0.50    0.11    -- -106.00  57.00   0.00   94
 18  \w   -117.00 -31.00   0.50    0.11    -- -106.00  19.00 -90.00  172
 19  \w   -113.00 -33.00   0.50    0.11    -- -106.00 125.00 -60.00  160
 20  \w    -77.00 -50.00   0.50    0.11    -- -106.00 155.00 -69.00   54
 21  \w   -105.00 -52.00   0.50    0.05    --  -47.45 155.00 -69.00  106
 22  \w   -109.00 -84.00   0.50    0.05    --  -47.45-155.00-108.00   50
 23  \w   -133.00-108.00   0.50    0.11    -- -106.00-155.00-108.00   50
 24  \w   -108.00 -71.00   0.50    0.11    -- -106.00-125.00 -60.00   74
 25  \w   -127.00-101.00   0.50    0.11    -- -106.00-119.00  48.00   52
 26  \w   -114.00 -74.00   0.50    0.05    --  -47.45-119.00  48.00   80
 27  \w   -119.00 -25.00   0.50    0.05    --  -47.45 -77.00  60.00  188
 28  \w   -120.00 -71.00   0.50    0.05    --  -47.45-125.00 150.00   98
 29  \w   -162.00-117.00   0.50    0.11    -- -106.00 -37.00 120.00   90
 30  \w   -172.00-110.00   0.50    0.11    -- -106.00 -37.00 150.00  124
 31  \w   -129.00 -41.00   0.50    0.11    -- -106.00  77.00 150.00  176
 32  \w   -129.00 -40.00   0.50    0.11    -- -106.00  77.00 -30.00  178
 33  \w   -131.00-102.00   0.50    0.11    -- -106.00 155.00 -69.00   58
 34  \w   -177.00-134.00   0.50    0.11    -- -106.00 -37.00 -60.00   86
 35  \w   -170.00 -92.00   0.50    0.11    -- -106.00 -77.00-120.00  156
 36  \w   -167.00-107.00   0.50    0.11    -- -106.00 -57.00  90.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1368409000
_diffrn_orient_matrix_UB_12      0.0110851000
_diffrn_orient_matrix_UB_13      -0.0002593000
_diffrn_orient_matrix_UB_21      -0.0304252000
_diffrn_orient_matrix_UB_22      -0.0459343000
_diffrn_orient_matrix_UB_23      -0.0741489000
_diffrn_orient_matrix_UB_31      -0.0368298000
_diffrn_orient_matrix_UB_32      -0.1055589000
_diffrn_orient_matrix_UB_33      0.0089273000
_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  0.1074
_diffrn_reflns_av_unetI/netI     0.0850
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            40125
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.531
_diffrn_reflns_theta_min         3.318
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.295
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45128
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.43a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.247
_exptl_crystal_description       block
_exptl_crystal_F_000             1266
_exptl_crystal_size_max          0.398
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.151
_refine_diff_density_max         1.192
_refine_diff_density_min         -0.877
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     748
_refine_ls_number_reflns         12709
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.126
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0728
_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^)+(0.1406P)^2^+0.9919P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2025
_refine_ls_wR_factor_ref         0.2335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10291
_reflns_number_total             12709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01394k2.cif
_cod_data_source_block           190519_tk01-120-1_thf
_cod_database_code               1566745
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C69 H76 O1 P2 Ni1'
_chemical_oxdiff_usercomment     '190519_TK01-120-1_THF C69 H76 O1 P2 Ni1'
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C12(H12), C2(H2), C24(H24), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C29(H29A,H29B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B),
 C15(H15A,H15B), C7(H7A,H7B), C3(H3A,H3B), C14(H14A,H14B), C23(H23A,H23B),
 C6(H6A,H6B), C19(H19A,H19B), C25(H25A,H25B), C16(H16A,H16B), C4(H4A,H4B),
 C21(H21A,H21B), C28(H28A,H28B), C22(H22A,H22B), C5(H5A,H5B), C20(H20A,H20B),
 C27(H27A,H27B), C26(H26A,H26B), C75(H75A,H75B), C76(H76A,H76B), C81(H81A,H81B),
  C82(H82A,H82B), C77(H77A,H77B)
2.c Aromatic/amide H refined with riding coordinates:
 C66(H66), C72(H72), C51(H51), C70(H70), C60(H60), C68(H68), C50(H50),
 C64(H64), C59(H59), C71(H71), C56(H56), C62(H62), C37(H37), C54(H54), C65(H65),
  C38(H38), C52(H52), C63(H63), C69(H69), C53(H53), C58(H58), C46(H46),
 C35(H35), C48(H48), C49(H49), C57(H57), C36(H36), C47(H47), C80(H80), C78(H78),
  C83(H83)
;
_shelx_res_checksum              47102
_shelx_hkl_checksum              74290
_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 2.634
_oxdiff_exptl_absorpt_empirical_full_min 0.355