Divergent synthesis of multi-substituted phenanthrenes <i>via</i> an internal redox reaction/ring expansion sequence.
Koyama, Ryosei; Anada, Masahiro; Sueki, Shunsuke; Makino, Kosho; Kojima, Tatsuhiro; Kawasaki-Takasuka, Tomoko; Mori, Keiji; Chemical communications (Cambridge, England) 60 (2024) 3822–3825; doi:10.1039/d4cc00797b

data_7132842
_publ_section_title
;
 Divergent synthesis of multi-substituted phenanthrenes <i>via</i> an
 internal redox reaction/ring expansion sequence.
;
_journal_issue                   28
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3822
_journal_page_last               3825
_journal_paper_doi               10.1039/d4cc00797b
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C18 H24 O2'
_chemical_formula_sum            'C18 H24 O2'
_chemical_formula_weight         272.37
_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
_audit_creation_date             2024-03-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-08 deposited with the CCDC.	2024-03-11 downloaded from the CCDC.
;
_cell_angle_alpha                105.1650(10)
_cell_angle_beta                 97.0650(10)
_cell_angle_gamma                105.2950(10)
_cell_formula_units_Z            4
_cell_length_a                   9.86400(10)
_cell_length_b                   9.86560(10)
_cell_length_c                   16.5931(2)
_cell_measurement_reflns_used    18573
_cell_measurement_temperature    101(1)
_cell_measurement_theta_max      68.0500
_cell_measurement_theta_min      2.8180
_cell_volume                     1471.00(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.88a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.992
_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    -66.00 -40.00   0.50    0.20    --  -42.87 110.00  82.00   52
  2  \w     23.00  48.00   0.50    0.20    --   42.87-110.00 -12.00   50
  3  \w   -124.00 -98.00   0.50    0.52    --  -80.25-110.00 -12.00   52
  4  \w    -82.00 -48.00   0.50    0.52    --  -80.25 110.00  82.00   68
  5  \w     59.00  94.00   0.50    0.52    --   94.32-110.00 -12.00   70
  6  \w    113.00 140.00   0.50    0.52    --   94.32 110.00  82.00   54
  7  \w    -52.00 -12.00   0.50    0.20    --   -8.00 124.00 117.69   80
  8  \w    -47.00  -9.00   0.50    0.20    --   -8.00 119.00  42.34   76
  9  \w    -30.00  -5.00   0.50    0.20    --    8.00 113.00 -35.83   50
 10  \w    -72.00 -24.00   0.50    0.20    --  -12.00 143.00-161.58   96
 11  \w    -13.00  13.00   0.50    0.20    --   20.00 102.00 130.23   52
 12  \w     -5.00  21.00   0.50    0.20    --   24.00  98.00-129.26   52
 13  \w     -4.00  21.00   0.50    0.20    --   28.00  98.00 -75.64   50
 14  \w     -4.00  21.00   0.50    0.20    --   28.00  99.00   9.48   50
 15  \w      0.00  25.00   0.50    0.20    --   32.00  98.00-163.05   50
 16  \w      0.00  25.00   0.50    0.20    --   32.00  98.00 -78.42   50
 17  \w      5.00  30.00   0.50    0.20    --   36.00  94.00  78.50   50
 18  \w      4.00  29.00   0.50    0.20    --   36.00  95.00 -35.96   50
 19  \w      9.00  34.00   0.50    0.20    --   40.00  94.00 111.52   50
 20  \w      9.00  34.00   0.50    0.20    --   40.00  94.00-154.28   50
 21  \w     11.00  38.00   0.50    0.20    --   40.00  88.00   1.46   54
 22  \w     54.00  90.00   0.50    0.20    --   42.87-138.00-180.00   72
 23  \w     15.00  40.00   0.50    0.20    --   44.00  88.00  98.41   50
 24  \w     14.00  39.00   0.50    0.20    --   44.00  91.00 -44.37   50
 25  \w     14.00  39.00   0.50    0.20    --   44.00  92.00  30.33   50
 26  \w     14.00  39.00   0.50    0.20    --   44.00  90.00 154.10   50
 27  \w     14.00  39.00   0.50    0.20    --   44.00  92.00 -97.02   50
 28  \w     14.00  39.00   0.50    0.20    --   44.00  92.00-140.59   50
 29  \w    -72.00 -27.00   0.50    0.20    --  -52.00 -77.00  59.77   90
 30  \w    -54.00 -29.00   0.50    0.20    --  -52.00 -71.00 -17.28   50
 31  \w    -56.00 -29.00   0.50    0.20    --  -52.00 -69.00 140.86   54
 32  \w    -54.00 -28.00   0.50    0.20    --  -52.00 -72.00-117.16   52
 33  \w   -108.00 -82.00   0.50    0.20    --  -52.00 -77.00  59.77   52
 34  \w     27.00  52.00   0.50    0.20    --   52.00  77.00 -82.77   50
 35  \w    -63.00 -37.00   0.50    0.20    --  -56.00 -63.00-166.38   52
 36  \w    -62.00 -33.00   0.50    0.20    --  -56.00 -71.00-130.17   58
 37  \w   -107.00 -81.00   0.50    0.20    --  -56.00 -71.00-130.17   52
 38  \w    -60.00 -34.00   0.50    0.20    --  -56.00 -73.00 104.90   52
 39  \w   -122.00 -91.00   0.50    0.20    --  -56.00 -73.00 130.56   62
 40  \w   -116.00 -91.00   0.50    0.20    --  -56.00 -72.00  25.67   50
 41  \w    -57.00 -32.00   0.50    0.20    --  -56.00 -72.00  25.67   50
 42  \w    -60.00 -32.00   0.50    0.20    --  -56.00 -73.00 130.56   56
 43  \w     31.00  57.00   0.50    0.20    --   56.00  77.00-126.55   52
 44  \w    -67.00 -37.00   0.50    0.20    --  -60.00 -72.00 -64.15   60
 45  \w   -112.00 -87.00   0.50    0.20    --  -60.00 -72.00 -64.15   50
 46  \w   -125.00-100.00   0.50    0.20    --  -60.00 -74.00 -70.73   50
 47  \w    -70.00 -36.00   0.50    0.20    --  -60.00 -74.00 -70.73   68
 48  \w   -106.00 -36.00   0.50    0.20    --  -60.00 -74.00 -15.25  140
 49  \w     40.00  70.00   0.50    0.20    --   64.00  76.00 128.87   60
 50  \w    -71.00 -41.00   0.50    0.20    --  -64.00 -76.00  21.52   60
 51  \w     94.00 128.00   0.50    0.20    --   64.00  76.00 128.87   68
 52  \w    -75.00 -43.00   0.50    0.20    --  -64.00 -69.00 -97.43   64
 53  \w    -65.00 -40.00   0.50    0.20    --  -64.00 -72.00 -41.12   50
 54  \w    -67.00 -40.00   0.50    0.20    --  -64.00 -76.00-153.53   54
 55  \w     47.00  73.00   0.50    0.20    --   68.00  77.00 -92.65   52
 56  \w    -74.00 -48.00   0.50    0.52    --  -72.00 -75.00-172.70   52
 57  \w    -74.00 -48.00   0.50    0.52    --  -72.00 -77.00  -5.53   52
 58  \w    -74.00 -47.00   0.50    0.52    --  -72.00 -77.00 -54.20   54
 59  \w   -119.00 -80.00   0.50    0.52    --  -72.00 -77.00 -54.20   78
 60  \w    -84.00 -47.00   0.50    0.52    --  -72.00 -76.00  13.06   74
 61  \w    -83.00 -51.00   0.50    0.52    --  -76.00 -76.00  39.14   64
 62  \w    -92.00 -51.00   0.50    0.52    --  -76.00 -76.00 126.71   82
 63  \w   -122.00 -96.00   0.50    0.52    --  -76.00 -76.00 126.71   52
 64  \w    -91.00 -51.00   0.50    0.52    --  -76.00 -76.00 148.94   80
 65  \w    -87.00 -52.00   0.50    0.52    --  -76.00 -74.00  51.41   70
 66  \w   -113.00 -55.00   0.50    0.52    --  -80.25 -77.00 120.00  116
 67  \w   -146.00 -56.00   0.50    0.52    --  -80.25 -77.00-180.00  180
 68  \w    -94.00 -55.00   0.50    0.52    --  -80.25 -77.00 -30.00   78
 69  \w    -91.00 -55.00   0.50    0.52    --  -80.25 -76.00 -72.07   72
 70  \w    -92.00 -57.00   0.50    0.52    --  -80.25 -77.00   0.00   70
 71  \w   -142.00-102.00   0.50    0.52    --  -80.25 -77.00   0.00   80
 72  \w    -86.00 -58.00   0.50    0.52    --  -80.25 -68.00  60.00   56
 73  \w    -90.00 -58.00   0.50    0.52    --  -80.25 -75.00  21.28   64
 74  \w    -84.00 -55.00   0.50    0.52    --  -80.25 -77.00 150.00   58
 75  \w   -141.00 -92.00   0.50    0.52    --  -80.25 -77.00-120.00   98
 76  \w    -81.00 -55.00   0.50    0.52    --  -80.25 -77.00-150.00   52
 77  \w   -142.00-116.00   0.50    0.52    --  -80.25 -77.00-150.00   52
 78  \w   -147.00 -55.00   0.50    0.52    --  -80.25 -77.00  90.00  184
 79  \w    -99.00 -55.00   0.50    0.52    --  -80.25 -77.00 -90.00   88
 80  \w    -85.00 -55.00   0.50    0.52    --  -80.25 -77.00-120.00   60
 81  \w   -128.00-102.00   0.50    0.52    --  -80.25 -77.00 -90.00   52
 82  \w     60.00  90.00   0.50    0.52    --   84.00  75.00   9.23   60
 83  \w     30.00  82.00   0.50    0.52    --   94.32 -68.00-120.00  104
 84  \w    108.00 159.00   0.50    0.52    --   94.32  68.00  55.95  102
 85  \w     72.00 104.00   0.50    0.52    --   94.32  68.00  55.95   64
 86  \w    114.00 158.00   0.50    0.52    --   94.32  42.00  90.00   88
 87  \w     35.00  60.00   0.50    0.52    --   94.32-117.00 -90.00   50
 88  \w     75.00 101.00   0.50    0.52    --   94.32  68.00 150.00   52
 89  \w     99.00 142.00   0.50    0.52    --   94.32 117.00-120.00   86
 90  \w     52.00 103.00   0.50    0.52    --   94.32-145.00-180.00  102
 91  \w     70.00 107.00   0.50    0.52    --   94.32  77.00 -90.00   74
 92  \w     70.00  95.00   0.50    0.52    --   94.32  77.00-150.00   50
 93  \w     72.00 157.00   0.50    0.52    --   94.32  77.00 150.00  170
 94  \w     26.00 104.00   0.50    0.52    --   94.32 -77.00   0.00  156
 95  \w     58.00 105.00   0.50    0.52    --   94.32 -96.00 150.00   94
 96  \w     70.00 156.00   0.50    0.52    --   94.32  77.00 120.00  172
 97  \w     72.00 161.00   0.50    0.52    --   94.32  68.00-180.00  178
 98  \w     72.00 115.00   0.50    0.52    --   94.32  77.00  90.00   86
 99  \w     72.00 108.00   0.50    0.52    --   94.32  68.00  30.00   72
100  \w    112.00 155.00   0.50    0.52    --   94.32  42.00  30.00   86
101  \w     36.00  69.00   0.50    0.52    --   94.32-117.00  90.00   66
102  \w    128.00 161.00   0.50    0.52    --   94.32  77.00  30.00   66
103  \w     35.00  80.00   0.50    0.52    --   94.32 -68.00 150.00   90
104  \w     71.00 119.00   0.50    0.52    --   94.32  77.00  30.00   96
105  \w     70.00 101.00   0.50    0.52    --   94.32  77.00 -30.00   62
106  \w    136.00 161.00   0.50    0.52    --   94.32  77.00  60.00   50
107  \w     70.00 112.00   0.50    0.52    --   94.32  77.00  60.00   84
108  \w     82.00 108.00   0.50    0.52    --   94.32-117.00  90.00   52
109  \w     29.00  68.00   0.50    0.52    --   94.32 -59.00 -90.00   78
110  \w     75.00 128.00   0.50    0.52    --   94.32  59.00 120.00  106
111  \w    102.00 155.00   0.50    0.52    --   94.32  68.00 -30.00  106
112  \w     30.00  55.00   0.50    0.52    --   94.32 -50.00   0.00   50
113  \w     31.00  56.00   0.50    0.52    --   94.32 -50.00  60.00   50
114  \w     70.00 134.00   0.50    0.52    --   94.32  77.00-120.00  128
115  \w     85.00 110.00   0.50    0.52    --   94.32-117.00-180.00   50
116  \w     30.00  60.00   0.50    0.52    --   94.32 -59.00  60.00   60
117  \w     72.00  98.00   0.50    0.52    --   94.32  68.00 -30.00   52
118  \w    116.00 154.00   0.50    0.52    --   94.32  77.00-150.00   76
119  \w     33.00  66.00   0.50    0.52    --   94.32-117.00-180.00   66
120  \w     34.00  78.00   0.50    0.52    --   94.32 -68.00-150.00   88
121  \w    104.00 137.00   0.50    0.52    --   94.32 117.00 -30.00   66
122  \w     78.00 136.00   0.50    0.52    --   94.32  59.00-150.00  116
123  \w    122.00 148.00   0.50    0.52    --   94.32  77.00 -60.00   52
124  \w     70.00 120.00   0.50    0.52    --   94.32  77.00 -60.00  100
125  \w    113.00 138.00   0.50    0.52    --   94.32  68.00 150.00   50
126  \w     61.00 108.00   0.50    0.52    --   94.32-117.00  30.00   94
127  \w     82.00 153.00   0.50    0.52    --   94.32  42.00 -60.00  142
128  \w    120.00 153.00   0.50    0.52    --   94.32  59.00-120.00   66
129  \w     79.00 108.00   0.50    0.52    --   94.32  59.00-120.00   58
130  \w     28.00  56.00   0.50    0.52    --   94.32 -50.00 -60.00   56
131  \w     93.00 119.00   0.50    0.52    --   94.32 -87.00-150.00   52
132  \w     30.00  79.00   0.50    0.52    --   94.32 -87.00-150.00   98
133  \w     75.00 154.00   0.50    0.52    --   94.32  68.00   0.00  158
134  \w     77.00 110.00   0.50    0.52    --   94.32-117.00 -90.00   66
135  \w    109.00 155.00   0.50    0.52    --   94.32  96.00 -60.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0206422000
_diffrn_orient_matrix_UB_12      -0.0522667000
_diffrn_orient_matrix_UB_13      0.0790902000
_diffrn_orient_matrix_UB_21      -0.0300927000
_diffrn_orient_matrix_UB_22      0.1370695000
_diffrn_orient_matrix_UB_23      0.0545406000
_diffrn_orient_matrix_UB_31      -0.1614000000
_diffrn_orient_matrix_UB_32      -0.0861329000
_diffrn_orient_matrix_UB_33      -0.0208411000
_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  0.0292
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            30651
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.314
_diffrn_reflns_theta_min         2.820
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.610
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.640
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.88a (Rigaku Oxford Diffraction, 2023)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.231
_refine_diff_density_min         -0.182
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     408
_refine_ls_number_reflns         5350
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0524P)^2^+0.4879P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1024
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4831
_reflns_number_total             5350
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00797b2.cif
_cod_data_source_block           koyamadiol_auto
_cod_depositor_comments
'Adding full bibliography for 7132841--7132842.cif.'
_cod_original_cell_volume        1470.99(3)
_cod_database_code               7132842
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C18H24O2
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.888
_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, All O(H) groups
2. Restrained distances
 H2A-O1
 2 with sigma of 0.02
 O2-C16 \\sim O2A-C16A
 with sigma of 0.02
 O4-C34 \\sim O4A-C34A
 with sigma of 0.02
 C19-C34 \\sim C19-C34A
 with sigma of 0.02
 O2-C1 \\sim O2A-C1
 with sigma of 0.04
 O4-C19 \\sim O4A-C19
 with sigma of 0.04
 C1-C16 \\sim C1-C16A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C19 \\sim C34A \\sim O4A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C1 \\sim C16A \\sim O2A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C34A) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C1, C16A, O2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(O2A)=Sof(H2A)=1-FVAR(1)
 Sof(O2)=Sof(H2)=Sof(C16)=Sof(H16A)=Sof(H16B)=FVAR(1)
 Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(O4A)=Sof(H4AA)=1-FVAR(2)
 Sof(O4)=Sof(H4)=Sof(C34)=Sof(H34A)=Sof(H34B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C24(H24)
6.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C32(H32A,H32B), C16(H16A,H16B), C33(H33A,
 H33B), C5(H5A,H5B), C4(H4A,H4B), C3(H3A,H3B), C34(H34A,H34B), C35(H35A,H35B),
 C21(H21A,H21B), C17(H17A,H17B), C23(H23A,H23B), C22(H22A,H22B), C16A(H16C,
 H16D), C34A(H34C,H34D)
6.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C30(H30), C28(H28), C29(H29), C12(H12), C10(H10), C11(H11), C9(H9)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C36(H36A,H36B,H36C)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4), O2A(H2A), O4A(H4AA)
;
_shelx_res_checksum              80857
_shelx_hkl_checksum              22675
_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 1.213
_oxdiff_exptl_absorpt_empirical_full_min 0.870