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_1563942
_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         'C19 H19 N O5'
_chemical_formula_sum            'C19 H19 N O5'
_chemical_formula_weight         341.35
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc27341k
_audit_creation_date             2020-10-22
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.54130(10)
_cell_length_b                   6.83260(10)
_cell_length_c                   38.8317(4)
_cell_measurement_reflns_used    22911
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      74.2310
_cell_measurement_theta_min      4.5070
_cell_volume                     1735.55(4)
_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      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -29.00  37.00   1.00    1.00    --    0.00  77.00   0.00   66
  2  \w     51.00  82.00   1.00    1.00    --    0.00  38.00 150.00   31
  3  \w     50.00  80.00   1.00    1.00    --    0.00  82.00  90.00   30
  4  \w    -18.00  80.00   1.00    1.00    --    0.00  38.00 -90.00   98
  5  \w    -12.00  47.00   1.00    1.00    --    0.00  82.00  90.00   59
  6  \w     51.00  88.00   1.00    1.00    --    0.00  38.00-180.00   37
  7  \w      9.00  35.00   1.00    1.00    --    0.00  38.00 150.00   26
  8  \w     44.00  70.00   1.00    1.00    --    0.00  57.00  90.00   26
  9  \w    -18.00  33.00   1.00    1.00    --    0.00  38.00-180.00   51
 10  \w    -23.00  15.00   1.00    1.00    --    0.00  19.00  60.00   38
 11  \w     11.00  84.00   1.00    1.00    --    0.00  57.00  30.00   73
 12  \w    -13.00  13.00   1.00    1.00    --    0.00  57.00  90.00   26
 13  \w     75.00 153.00   1.00    1.00    --   95.80  45.00 -60.00   78
 14  \w     66.00  92.00   1.00    1.00    --   95.80  75.00  54.64   26
 15  \w     67.00 118.00   1.00    1.00    --   95.80  71.00 153.28   51
 16  \w    159.00 184.00   1.00    1.00    --   95.80  82.00 129.00   25
 17  \w    113.00 156.00   1.00    1.00    --   95.80  82.00 129.00   43
 18  \w     64.00 132.00   1.00    1.00    --   95.80  79.00 161.26   68
 19  \w    131.00 156.00   1.00    1.00    --   95.80  66.00  38.05   25
 20  \w     75.00 101.00   1.00    1.00    --   95.80  61.00 120.00   26
 21  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-180.00   26
 22  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 129.00   25
 23  \w    153.00 180.00   1.00    1.00    --   95.80  61.00 120.00   27
 24  \w      7.00 128.00   1.00    1.00    --   95.80 -82.00 150.00  121
 25  \w     68.00  94.00   1.00    1.00    --   95.80  82.00-180.00   26
 26  \w     67.00  92.00   1.00    1.00    --   95.80  82.00 -90.00   25
 27  \w     64.00  94.00   1.00    1.00    --   95.80  82.00-120.00   30
 28  \w     73.00  99.00   1.00    1.00    --   95.80  61.00-120.00   26
 29  \w    134.00 168.00   1.00    1.00    --   95.80  61.00-120.00   34
 30  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 31  \w    117.00 143.00   1.00    1.00    --   95.80  77.00 -60.00   26
 32  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   26
 33  \w     65.00 181.00   1.00    1.00    --   95.80  77.00  -9.43  116
 34  \w    133.00 159.00   1.00    1.00    --   95.80  71.00-149.61   26
 35  \w     63.00  95.00   1.00    1.00    --   95.80  82.00  60.00   32
 36  \w     45.00 123.00   1.00    1.00    --   95.80 -82.00  30.00   78
 37  \w     43.00 103.00   1.00    1.00    --   95.80 -82.00 -60.00   60
 38  \w     15.00  41.00   1.00    1.00    --   95.80 -82.00  30.00   26
 39  \w    117.00 144.00   1.00    1.00    --   95.80  82.00  60.00   27
 40  \w     71.00 102.00   1.00    1.00    --   95.80  61.00-150.00   31
 41  \w     66.00  92.00   1.00    1.00    --   95.80  77.00-150.00   26
 42  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 43  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 44  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 45  \w    113.00 185.00   1.00    1.00    --   95.80  82.00 -30.00   72
 46  \w     65.00  99.00   1.00    1.00    --   95.80  77.00  90.00   34
 47  \w    114.00 181.00   1.00    1.00    --   95.80  45.00 -90.00   67
 48  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 120.00   25
 49  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 50  \w    116.00 174.00   1.00    1.00    --   95.80  74.00  83.40   58
 51  \w     44.00 127.00   1.00    1.00    --   95.80 -82.00-120.00   83
 52  \w    130.00 155.00   1.00    1.00    --   95.80  45.00 -30.00   25
 53  \w    109.00 182.00   1.00    1.00    --   95.80  82.00-180.00   73
 54  \w     63.00  90.00   1.00    1.00    --   95.80  82.00-150.00   27
 55  \w     75.00 184.00   1.00    1.00    --   95.80  45.00-150.00  109
 56  \w     78.00 166.00   1.00    1.00    --   95.80  45.00 150.00   88
 57  \w     71.00 105.00   1.00    1.00    --   95.80  61.00 -30.00   34
 58  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 59  \w    107.00 184.00   1.00    1.00    --   95.80  77.00  30.00   77
 60  \w     71.00 180.00   1.00    1.00    --   95.80  61.00  60.00  109
 61  \w     62.00 117.00   1.00    1.00    --   95.80 -61.00  30.00   55
 62  \w     75.00 108.00   1.00    1.00    --   95.80  45.00 -90.00   33
 63  \w     75.00 101.00   1.00    1.00    --   95.80  45.00 -30.00   26
 64  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 65  \w     73.00  98.00   1.00    1.00    --   95.80 -82.00 120.00   25
 66  \w     66.00  92.00   1.00    1.00    --   95.80  74.00  83.40   26
 67  \w     68.00  94.00   1.00    1.00    --   95.80  71.00-149.61   26
 68  \w     69.00  95.00   1.00    1.00    --   95.80  66.00  38.05   26
 69  \w     71.00  97.00   1.00    1.00    --   95.80  59.00 -12.51   26
;
_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      0.0359993000
_diffrn_orient_matrix_UB_12      0.2105099000
_diffrn_orient_matrix_UB_13      0.0128707000
_diffrn_orient_matrix_UB_21      0.0321992000
_diffrn_orient_matrix_UB_22      -0.0777313000
_diffrn_orient_matrix_UB_23      0.0368466000
_diffrn_orient_matrix_UB_31      0.2304739000
_diffrn_orient_matrix_UB_32      -0.0219861000
_diffrn_orient_matrix_UB_33      -0.0071384000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_unetI/netI     0.0140
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            37967
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.069
_diffrn_reflns_theta_max         67.069
_diffrn_reflns_theta_min         4.555
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.787
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52906
_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    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.102
_refine_diff_density_min         -0.134
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1218 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         3095
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0246
_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^)+(0.0307P)^2^+0.3626P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0626
_refine_ls_wR_factor_ref         0.0628
_reflns_Friedel_coverage         0.677
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                3069
_reflns_number_total             3095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02119b2.cif
_cod_data_source_block           exp_1488
_cod_database_code               1563942
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7)
2.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C18(H18), C15(H15), C19(H19), C2(H2), C3(H3)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              68158
_shelx_hkl_checksum              11415
_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 2.690
_oxdiff_exptl_absorpt_empirical_full_min 0.595