Catalytic Enantioselective Synthesis of Benzocyclobutenols and Cyclobutanols via A Sequential Reduction/C-H Functionalization
Chen, Jun; Shi, Zhan; Li, Chunyu; Lu, Ping; Chemical Science  (2021) –; doi:10.1039/D1SC02119B

data_1563945
_publ_section_title
;
 Catalytic Enantioselective Synthesis of Benzocyclobutenols and
 Cyclobutanols via A Sequential Reduction/C-H Functionalization
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02119B
_journal_year                    2021
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C22 H24 N2 O6 S'
_chemical_formula_sum            'C22 H24 N2 O6 S'
_chemical_formula_weight         444.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc27342l
_audit_creation_date             2020-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-01-24 deposited with the CCDC.	2021-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.2200(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.53540(10)
_cell_length_b                   10.51100(10)
_cell_length_c                   18.55590(10)
_cell_measurement_reflns_used    33479
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.0310
_cell_measurement_theta_min      3.5380
_cell_volume                     2419.80(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.992
_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    -24.00  29.00   1.00    1.00    --    0.00 -77.00-180.00   53
  2  \w    -71.00 -34.00   1.00    1.00    --    0.00 -57.00 -60.00   37
  3  \w     52.00  81.00   1.00    1.00    --    0.00  38.00 -30.00   29
  4  \w     -5.00  45.00   1.00    1.00    --    0.00  38.00 -30.00   50
  5  \w    -83.00 -34.00   1.00    1.00    --    0.00 -77.00-180.00   49
  6  \w    -73.00 -46.00   1.00    1.00    --    0.00 -19.00   0.00   27
  7  \w    -81.00  23.00   1.00    1.00    --    0.00 -57.00-150.00  104
  8  \w    -31.00  23.00   1.00    1.00    --    0.00 -57.00 -60.00   54
  9  \w    -19.00  20.00   1.00    1.00    --    0.00 -19.00   0.00   39
 10  \w    -88.00  18.00   1.00    1.00    --    0.00 -38.00  90.00  106
 11  \w    -18.00  65.00   1.00    1.00    --    0.00  38.00  90.00   83
 12  \w     96.00 122.00   1.00    1.00    --   95.80  76.00 -30.05   26
 13  \w     64.00  92.00   1.00    1.00    --   95.80  80.00-127.74   28
 14  \w     72.00  98.00   1.00    1.00    --   95.80  61.00 120.00   26
 15  \w     65.00  90.00   1.00    1.00    --   95.80  76.00 -30.05   25
 16  \w    133.00 175.00   1.00    1.00    --   95.80  78.00  53.16   42
 17  \w     69.00 100.00   1.00    1.00    --   95.80  66.00-140.20   31
 18  \w     72.00 185.00   1.00    1.00    --   95.80  55.00-164.45  113
 19  \w     71.00  97.00   1.00    1.00    --   95.80  61.00-150.00   26
 20  \w     65.00  91.00   1.00    1.00    --   95.80  78.00  53.16   26
 21  \w     10.00 128.00   1.00    1.00    --   95.80 -82.00   0.00  118
 22  \w     57.00 126.00   1.00    1.00    --   95.80 -82.00-180.00   69
 23  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 24  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 25  \w     75.00 180.00   1.00    1.00    --   95.80  45.00  30.00  105
 26  \w    140.00 166.00   1.00    1.00    --   95.80  82.00-120.00   26
 27  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 28  \w     63.00  98.00   1.00    1.00    --   95.80  82.00 120.00   35
 29  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 30  \w      7.00 119.00   1.00    1.00    --   95.80 -82.00 150.00  112
 31  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 32  \w    143.00 185.00   1.00    1.00    --   95.80  75.00 -65.29   42
 33  \w    126.00 179.00   1.00    1.00    --   95.80  74.00 -39.08   53
 34  \w     95.00 127.00   1.00    1.00    --   95.80 -82.00  30.00   32
 35  \w     71.00 185.00   1.00    1.00    --   95.80  61.00  90.00  114
 36  \w     53.00  79.00   1.00    1.00    --   95.80 -82.00  30.00   26
 37  \w    103.00 185.00   1.00    1.00    --   95.80  82.00  30.00   82
 38  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-180.00   25
 39  \w     75.00 179.00   1.00    1.00    --   95.80  45.00-180.00  104
 40  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 41  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 42  \w    146.00 172.00   1.00    1.00    --   95.80  82.00 150.00   26
 43  \w     66.00  91.00   1.00    1.00    --   95.80  75.00 -65.29   25
 44  \w     73.00 123.00   1.00    1.00    --   95.80  61.00 -60.00   50
 45  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-150.00   25
 46  \w    121.00 182.00   1.00    1.00    --   95.80  82.00-150.00   61
 47  \w     76.00 163.00   1.00    1.00    --   95.80  45.00 150.00   87
 48  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  30.00   25
 49  \w     91.00 128.00   1.00    1.00    --   95.80 -82.00-150.00   37
 50  \w     71.00  96.00   1.00    1.00    --   95.80  61.00  30.00   25
 51  \w     65.00  90.00   1.00    1.00    --   95.80  77.00   0.00   25
 52  \w     63.00  97.00   1.00    1.00    --   95.80  82.00-120.00   34
 53  \w     21.00  74.00   1.00    1.00    --   95.80 -82.00-150.00   53
 54  \w     71.00  97.00   1.00    1.00    --   95.80  61.00   0.00   26
 55  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 56  \w     76.00 175.00   1.00    1.00    --   95.80  45.00 -60.00   99
 57  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 58  \w    148.00 174.00   1.00    1.00    --   95.80  61.00 120.00   26
 59  \w    122.00 179.00   1.00    1.00    --   95.80  80.00-127.74   57
 60  \w     48.00 123.00   1.00    1.00    --   95.80 -82.00 -30.00   75
 61  \w     66.00  91.00   1.00    1.00    --   95.80  74.00 -39.08   25
 62  \w     70.00  96.00   1.00    1.00    --   95.80  64.00  41.79   26
 63  \w     75.00 107.00   1.00    1.00    --   95.80  45.00 -90.00   32
 64  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 65  \w     71.00 112.00   1.00    1.00    --   95.80  61.00 -30.00   41
 66  \w     74.00 184.00   1.00    1.00    --   95.80  53.00  70.10  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1077786000
_diffrn_orient_matrix_UB_12      0.0391991000
_diffrn_orient_matrix_UB_13      0.0242733000
_diffrn_orient_matrix_UB_21      -0.0583111000
_diffrn_orient_matrix_UB_22      -0.0253078000
_diffrn_orient_matrix_UB_23      -0.0774897000
_diffrn_orient_matrix_UB_31      -0.0198192000
_diffrn_orient_matrix_UB_32      -0.1390208000
_diffrn_orient_matrix_UB_33      0.0209672000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0540
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            56015
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         4.848
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.510
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53719
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.220
_exptl_crystal_description       plate
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.155
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 3580 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         8412
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0309
_refine_ls_R_factor_gt           0.0300
_refine_ls_shift/su_max          0.021
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0438P)^2^+0.1725P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0789
_refine_ls_wR_factor_ref         0.0795
_reflns_Friedel_coverage         0.850
_reflns_Friedel_fraction_full    0.949
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                8106
_reflns_number_total             8412
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02119b2.cif
_cod_data_source_block           exp_1546
_cod_database_code               1563945
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.852
_shelx_estimated_absorpt_t_min   0.612
_reflns_odcompleteness_completeness 99.98
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C33(H33), C11(H11), C9(H9), C31(H31), C12(H12), C34(H34)
2.b Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C8(H8A,H8B), C13(H13A,H13B), C35(H35A,H35B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C44(H44), C22(H22), C43(H43), C24(H24), C5(H5), C21(H21), C2(H2),
 C40(H40), C28(H28), C18(H18), C25(H25), C41(H41), C19(H19), C3(H3), C27(H27)
2.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C37(H37A,H37B,
 H37C), C7(H7A,H7B,H7C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              95249
_shelx_hkl_checksum              14511
_shelx_fab_checksum              58522
_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 2.180
_oxdiff_exptl_absorpt_empirical_full_min 0.585