Two-Carbon Ring Expansion of Cyclobutanols to Cyclohexenones Enabled by Indole Radical Cation Intermediate: Development and Application to a Total Synthesis of Uleine
Leclair, Alexandre; Wang, Qian; Zhu, Jieping; ACS Catalysis 12 (2022) 1209–1215; doi:10.1021/acscatal.1c05621

data_4519304
_publ_section_title
;
 Two-Carbon Ring Expansion of Cyclobutanols to Cyclohexenones Enabled by
 Indole Radical Cation Intermediate: Development and Application to a
 Total Synthesis of Uleine
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              1209
_journal_page_last               1215
_journal_paper_doi               10.1021/acscatal.1c05621
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C16 H15 N O'
_chemical_formula_sum            'C16 H15 N O'
_chemical_formula_weight         237.29
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_cell_angle_alpha                75.423(2)
_cell_angle_beta                 85.496(2)
_cell_angle_gamma                84.466(2)
_cell_formula_units_Z            2
_cell_length_a                   4.86815(14)
_cell_length_b                   8.4796(3)
_cell_length_c                   15.0305(4)
_cell_measurement_reflns_used    9883
_cell_measurement_temperature    140.01(10)
_cell_measurement_theta_max      76.3770
_cell_measurement_theta_min      5.4460
_cell_volume                     596.74(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (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 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.01(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 0.982
_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    -70.00 -45.00   1.00    1.00    --  -43.01 159.00 -94.00   25
  2  \w    -79.00 -54.00   1.00    1.00    --  -43.01-159.00-126.00   25
  3  \w    -82.00   0.00   1.00    1.00    --  -43.01 118.00 112.00   82
  4  \w     23.00  88.00   1.00    1.00    --   43.01-118.00  25.00   65
  5  \w     54.00 109.00   1.00    4.00    --  112.00-118.00  25.00   55
  6  \w     93.00 120.00   1.00    4.00    --  112.00 159.00 -94.00   27
  7  \w    115.00 140.00   1.00    4.00    --  112.00 118.00 112.00   25
  8  \w     90.00 127.00   1.00    4.00    --  112.00-159.00-126.00   37
  9  \w      1.00  26.00   1.00    1.00    --   38.00  90.00  94.44   25
 10  \w      3.00  28.00   1.00    1.00    --   38.00  88.00  12.66   25
 11  \w      9.00  34.00   1.00    1.00    --   42.00  77.00 151.65   25
 12  \w      9.00  34.00   1.00    1.00    --   42.00  78.00 -54.74   25
 13  \w      9.00  34.00   1.00    1.00    --   42.00  83.00 170.97   25
 14  \w     16.00  42.00   1.00    1.00    --   42.00  82.00  30.22   26
 15  \w   -115.00 -89.00   1.00    1.00    --  -43.01 -19.00-150.00   26
 16  \w    -61.00  -4.00   1.00    1.00    --  -43.01 -19.00-150.00   57
 17  \w   -116.00 -55.00   1.00    1.00    --  -43.01 -37.00  60.00   61
 18  \w    -49.00 -21.00   1.00    1.00    --  -43.01 -37.00  60.00   28
 19  \w     13.00  38.00   1.00    1.00    --   46.00  82.00 -94.15   25
 20  \w     16.00  41.00   1.00    1.00    --   50.00  81.00 115.32   25
 21  \w     16.00  41.00   1.00    1.00    --   50.00  82.00-169.38   25
 22  \w     16.00  41.00   1.00    1.00    --   50.00  81.00 -21.80   25
 23  \w     16.00  41.00   1.00    1.00    --   50.00  81.00 -55.15   25
 24  \w    108.00 133.00   1.00    1.00    --   58.00  73.00-140.81   25
 25  \w     31.00  61.00   1.00    1.00    --   58.00  73.00-140.81   30
 26  \w     34.00  96.00   1.00    1.00    --   58.00  50.00  47.93   62
 27  \w     30.00  73.00   1.00    1.00    --   62.00  74.00 -63.79   43
 28  \w     84.00 110.00   1.00    1.00    --   62.00  74.00 -63.79   26
 29  \w    110.00 135.00   1.00    1.00    --   62.00  45.00  24.72   25
 30  \w     31.00  59.00   1.00    1.00    --   62.00  72.00-109.84   28
 31  \w     37.00  68.00   1.00    1.00    --   62.00  45.00  24.72   31
 32  \w     99.00 124.00   1.00    1.00    --   62.00  72.00-109.84   25
 33  \w     36.00  72.00   1.00    1.00    --   66.00  71.00 162.93   36
 34  \w     39.00  67.00   1.00    1.00    --   70.00  69.00-166.75   28
 35  \w    118.00 143.00   1.00    1.00    --   70.00  69.00  94.19   25
 36  \w     40.00  73.00   1.00    1.00    --   70.00  69.00  94.19   33
 37  \w     49.00  75.00   1.00    1.00    --   74.00  61.00 132.78   26
 38  \w     89.00 114.00   1.00    1.00    --   74.00  61.00 132.78   25
 39  \w    116.00 151.00   1.00    4.00    --   78.00  74.00  26.64   35
 40  \w     47.00  82.00   1.00    4.00    --   78.00  74.00  26.64   35
 41  \w    109.00 139.00   1.00    4.00    --   78.00  51.00-117.29   30
 42  \w     53.00 105.00   1.00    4.00    --   78.00  51.00-117.29   52
 43  \w     70.00  97.00   1.00    4.00    --   82.00  56.00 -41.39   27
 44  \w     50.00  78.00   1.00    4.00    --   82.00  74.00 -93.75   28
 45  \w     58.00  84.00   1.00    4.00    --   86.00  59.00  61.41   26
 46  \w     60.00 100.00   1.00    4.00    --   90.00  71.00 -10.36   40
 47  \w     69.00 100.00   1.00    4.00    --   98.00  68.00 -73.01   31
 48  \w     72.00  98.00   1.00    4.00    --   98.00  59.00  61.82   26
 49  \w    119.00 145.00   1.00    4.00    --   98.00  59.00  61.82   26
 50  \w     40.00 109.00   1.00    4.00    --  112.00-111.00  60.00   69
 51  \w    118.00 177.00   1.00    4.00    --  112.00  61.00-150.00   59
 52  \w     87.00 112.00   1.00    4.00    --  112.00  61.00 -30.00   25
 53  \w     85.00 111.00   1.00    4.00    --  112.00  61.00-150.00   26
 54  \w     84.00 169.00   1.00    4.00    --  112.00  61.00 150.00   85
 55  \w     88.00 120.00   1.00    4.00    --  112.00  45.00  90.00   32
 56  \w    127.00 173.00   1.00    4.00    --  112.00  61.00-120.00   46
 57  \w     71.00 131.00   1.00    4.00    --  112.00 178.00  60.00   60
 58  \w    119.00 163.00   1.00    4.00    --  112.00  61.00  60.00   44
 59  \w     84.00 112.00   1.00    4.00    --  112.00  61.00-120.00   28
 60  \w     83.00 111.00   1.00    4.00    --  112.00  61.00  60.00   28
 61  \w     83.00 168.00   1.00    4.00    --  112.00  61.00-180.00   85
 62  \w     96.00 138.00   1.00    4.00    --  112.00  45.00 -90.00   42
 63  \w     40.00 123.00   1.00    4.00    --  112.00 -45.00-180.00   83
 64  \w     93.00 120.00   1.00    4.00    --  112.00  45.00 -30.00   27
 65  \w     50.00 127.00   1.00    4.00    --  112.00 -61.00  30.00   77
 66  \w     58.00 144.00   1.00    4.00    --  112.00 -77.00-180.00   86
 67  \w    122.00 173.00   1.00    4.00    --  112.00  61.00  30.00   51
 68  \w     84.00 112.00   1.00    4.00    --  112.00  61.00  30.00   28
 69  \w     84.00 167.00   1.00    4.00    --  112.00  61.00   0.00   83
 70  \w     41.00 102.00   1.00    4.00    --  112.00-111.00-150.00   61
 71  \w    116.00 163.00   1.00    4.00    --  112.00  61.00 -60.00   47
 72  \w     83.00 178.00   1.00    4.00    --  112.00  61.00  90.00   95
 73  \w     84.00 111.00   1.00    4.00    --  112.00  61.00 -60.00   27
 74  \w    130.00 178.00   1.00    4.00    --  112.00  61.00 -90.00   48
 75  \w     84.00 114.00   1.00    4.00    --  112.00  56.00 142.67   30
 76  \w     85.00 112.00   1.00    4.00    --  112.00  61.00 -90.00   27
 77  \w     83.00 132.00   1.00    4.00    --  112.00  61.00 120.00   49
 78  \w    118.00 175.00   1.00    4.00    --  112.00  61.00 -30.00   57
;
_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      0.0263486000
_diffrn_orient_matrix_UB_12      0.1509712000
_diffrn_orient_matrix_UB_13      0.0372811000
_diffrn_orient_matrix_UB_21      0.0187166000
_diffrn_orient_matrix_UB_22      -0.1105780000
_diffrn_orient_matrix_UB_23      0.0981805000
_diffrn_orient_matrix_UB_31      0.3168001000
_diffrn_orient_matrix_UB_32      -0.0210657000
_diffrn_orient_matrix_UB_33      -0.0149060000
_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  0.0104
_diffrn_reflns_av_unetI/netI     0.0061
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            11736
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.505
_diffrn_reflns_theta_min         3.043
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.645
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.654
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       prism
_exptl_crystal_F_000             252
_exptl_crystal_size_max          0.99
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.266
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.012(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     166
_refine_ls_number_reflns         2458
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0346
_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^)+(0.0452P)^2^+0.1944P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0879
_refine_ls_wR_factor_ref         0.0887
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2377
_reflns_number_total             2458
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05621_si_002.cif
_cod_data_source_block           al-07-082
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               4519304
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C16 H15 N O'
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.568
_reflns_odcompleteness_completeness 99.34
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H,H,H) groups
2. Others
 Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(1)
 Sof(H16D)=Sof(H16E)=Sof(H16F)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C4(H4), C8(H8)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C7(H7A,H7B)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C11(H11), C12(H12), C13(H13), C14(H14)
3.d Disordered Me refined as rotating group:
 C16(H16A,H16B,H16C,H16D,H16E,H16F)
;
_shelx_res_checksum              95979
_shelx_hkl_checksum              21117
_olex2_date_sample_data_collection 2020-12-08
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.422
_oxdiff_exptl_absorpt_empirical_full_min 0.823