Cu(ii)/SPDO complex catalyzed asymmetric Baeyer-Villiger oxidation of 2-arylcyclobutanones and its application for the total synthesis of eupomatilones 5 and 6.
Zhang, Chang-Sheng; Shao, Ya-Ping; Zhang, Fu-Min; Han, Xue; Zhang, Xiao-Ming; Zhang, Kun; Tu, Yong-Qiang; Chemical science 13 (2022) 8429–8435; doi:10.1039/d2sc02079c

data_1567165
_publ_section_title
;
 Cu(ii)/SPDO complex catalyzed asymmetric Baeyer-Villiger oxidation of
 2-arylcyclobutanones and its application for the total synthesis of
 eupomatilones 5 and 6.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              8429
_journal_page_last               8435
_journal_paper_doi               10.1039/d2sc02079c
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H14 O2'
_chemical_formula_sum            'C16 H14 O2'
_chemical_formula_weight         238.27
_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_creation_date             2022-04-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-04-28 deposited with the CCDC.	2022-06-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.2470(2)
_cell_length_b                   8.2089(2)
_cell_length_c                   28.1307(9)
_cell_measurement_reflns_used    4958
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      73.1610
_cell_measurement_theta_min      3.1860
_cell_volume                     1211.65(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.975
_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     62.00 116.00   1.00    0.12    --   47.45  57.00-150.00   54
  2  \w    126.00 152.00   1.00    0.40    --  107.75  37.00 -60.00   26
  3  \w    146.00 172.00   1.00    0.40    --  107.75  37.00-180.00   26
  4  \w    102.00 128.00   1.00    0.40    --  107.75  37.00-180.00   26
  5  \w    -21.00   5.00   1.00    0.12    --   47.45 -19.00 -60.00   26
  6  \w    -19.00  15.00   1.00    0.12    --   47.45 -19.00-150.00   34
  7  \w     37.00  63.00   1.00    0.40    --  107.75-125.00 -60.00   26
  8  \w     37.00  63.00   1.00    0.40    --  107.75-125.00-180.00   26
  9  \w     76.00 108.00   1.00    0.40    --  107.75-109.00-144.00   32
 10  \w     86.00 112.00   1.00    0.40    --  107.75-125.00 -60.00   26
 11  \w     80.00 106.00   1.00    0.40    --  107.75 -99.00   0.00   26
 12  \w     -9.00  33.00   1.00    0.12    --   47.45 -49.00  98.00   42
 13  \w     30.00 108.00   1.00    0.12    --   47.45-150.00  66.00   78
 14  \w     58.00  99.00   1.00    0.40    --  107.75 -99.00  90.00   41
 15  \w     72.00 100.00   1.00    0.40    --  107.75 -77.00  90.00   28
 16  \w     35.00  62.00   1.00    0.40    --  107.75 -57.00 -60.00   27
 17  \w     51.00 102.00   1.00    0.40    --  107.75 -77.00-150.00   51
 18  \w     37.00  62.00   1.00    0.40    --  107.75 -57.00-180.00   25
 19  \w   -105.00 -71.00   1.00    0.40    -- -100.00 109.00 -48.00   34
 20  \w   -104.00 -40.00   1.00    0.40    -- -100.00 122.00 -49.00   64
 21  \w    -63.00 -37.00   1.00    0.40    -- -100.00 125.00-120.00   26
 22  \w   -112.00 -76.00   1.00    0.40    -- -100.00 125.00-120.00   36
 23  \w    -67.00 -29.00   1.00    0.40    -- -100.00 125.00  90.00   38
 24  \w   -112.00 -86.00   1.00    0.40    -- -100.00 125.00  90.00   26
 25  \w    -83.00 -29.00   1.00    0.40    -- -100.00  72.00  68.00   54
 26  \w    -69.00 -44.00   1.00    0.40    -- -100.00  57.00 -30.00   25
 27  \w    -53.00 -27.00   1.00    0.40    -- -100.00  57.00 -90.00   26
 28  \w    -54.00 -28.00   1.00    0.40    -- -100.00  49.00-114.00   26
 29  \w   -171.00 -97.00   1.00    0.40    -- -100.00 -19.00   0.00   74
 30  \w   -170.00-131.00   1.00    0.40    -- -100.00 -37.00   0.00   39
 31  \w   -161.00 -80.00   1.00    0.40    -- -100.00 -72.00 -61.00   81
 32  \w   -123.00 -97.00   1.00    0.40    -- -100.00 -37.00   0.00   26
 33  \w   -168.00-141.00   1.00    0.40    -- -100.00 -49.00  98.00   27
 34  \w   -173.00-135.00   1.00    0.40    -- -100.00 -37.00 150.00   38
 35  \w   -122.00 -96.00   1.00    0.40    -- -100.00 -37.00 150.00   26
 36  \w   -113.00 -88.00   1.00    0.40    -- -100.00 -49.00  98.00   25
 37  \w   -123.00 -94.00   1.00    0.40    -- -100.00 -99.00  90.00   29
 38  \w   -165.00-132.00   1.00    0.40    -- -100.00 -99.00  90.00   33
 39  \w   -165.00 -77.00   1.00    0.40    -- -100.00-150.00  66.00   88
 40  \w   -117.00 -66.00   1.00    0.12    --  -47.45-150.00  66.00   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0024211000
_diffrn_orient_matrix_UB_12      0.1498838000
_diffrn_orient_matrix_UB_13      0.0329667000
_diffrn_orient_matrix_UB_21      -0.2921600000
_diffrn_orient_matrix_UB_22      0.0099163000
_diffrn_orient_matrix_UB_23      -0.0045271000
_diffrn_orient_matrix_UB_31      -0.0288140000
_diffrn_orient_matrix_UB_32      -0.1126416000
_diffrn_orient_matrix_UB_33      0.0434698000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0166
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            2834
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.956
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.403
_diffrn_reflns_theta_min         3.142
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.679
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78142
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
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             504
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.318
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.3(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     164
_refine_ls_number_reflns         2834
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.112
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0687
_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^)+(0.1504P)^2^+0.0769P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1927
_refine_ls_wR_factor_ref         0.1994
_reflns_Friedel_coverage         0.642
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                2623
_reflns_number_total             2834
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.2392\% 
around [0.02 -0.00 1.00] (reciprocal) or [0.40 -0.02 0.92] (direct)
;
_cod_data_source_file            d2sc02079c3.cif
_cod_data_source_block           zhangchsh_0412_3_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1567165--1567169.cif.'
_cod_database_code               1567165
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.504(7)
 0.496(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C13(H13)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11)
;
_shelx_res_checksum              40423
_shelx_hkl_checksum              69723
_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 3.656
_oxdiff_exptl_absorpt_empirical_full_min 0.344
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2