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_1567168
_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         'C14 H12 O2'
_chemical_formula_sum            'C14 H12 O2'
_chemical_formula_weight         212.23
_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             2021-12-06
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6427)
;
_audit_update_record
;
2022-04-04 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            8
_cell_length_a                   8.67930(10)
_cell_length_b                   22.7043(3)
_cell_length_c                   11.04130(10)
_cell_measurement_reflns_used    9071
_cell_measurement_temperature    298.23(10)
_cell_measurement_theta_max      75.3670
_cell_measurement_theta_min      1.9490
_cell_volume                     2175.77(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.23(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.965
_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     92.00 175.00   0.50    0.05    --  109.26  47.00   0.00  166
  2  \w    136.00 170.00   0.50    0.05    --  109.26  30.00 -60.00   68
  3  \w    135.00 173.00   0.50    0.05    --  109.26  45.00 -90.00   76
  4  \w     98.00 125.00   0.50    0.05    --  109.26  30.00 -60.00   54
  5  \w     44.00  70.00   0.50    0.05    --  109.26 -77.00   0.00   52
  6  \w     38.00  67.00   0.50    0.05    --  109.26 -61.00 150.00   58
  7  \w    -19.00  14.00   0.50    0.05    --   43.05 -19.00  90.00   66
  8  \w    -11.00  15.00   0.50    0.05    --   43.05 -19.00-150.00   52
  9  \w     35.00  67.00   0.50    0.05    --  109.26 -61.00-180.00   64
 10  \w    -51.00 -24.00   0.50    0.05    -- -100.00  45.00  60.00   54
 11  \w    -74.00 -27.00   0.50    0.05    -- -100.00  61.00 120.00   94
 12  \w    -54.00 -29.00   0.50    0.05    -- -100.00  45.00 150.00   50
 13  \w    -53.00 -24.00   0.50    0.05    -- -100.00  45.00 120.00   58
 14  \w    -51.00 -24.00   0.50    0.05    -- -100.00  45.00  90.00   54
 15  \w    -73.00 -27.00   0.50    0.05    -- -100.00  79.00 135.00   92
 16  \w   -127.00-100.00   0.50    0.05    -- -100.00  79.00 135.00   54
 17  \w    -24.00  35.00   0.50    0.05    --  -43.05  19.00 120.00  118
 18  \w    -55.00  32.00   0.50    0.05    --  -43.05  47.00   0.00  174
 19  \w    -96.00 -37.00   0.50    0.05    -- -100.00 104.00-135.00  118
 20  \w     37.00  93.00   0.50    0.05    --  109.26 -94.00-120.00  112
 21  \w   -115.00 -90.00   0.50    0.05    --  -43.05-179.00-180.00   50
;
_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      0.0288311000
_diffrn_orient_matrix_UB_12      0.0650141000
_diffrn_orient_matrix_UB_13      -0.0330433000
_diffrn_orient_matrix_UB_21      -0.0993254000
_diffrn_orient_matrix_UB_22      -0.0073627000
_diffrn_orient_matrix_UB_23      -0.1146734000
_diffrn_orient_matrix_UB_31      -0.1441476000
_diffrn_orient_matrix_UB_32      0.0180867000
_diffrn_orient_matrix_UB_33      0.0723015000
_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  0.0235
_diffrn_reflns_av_unetI/netI     0.0235
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11192
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.912
_diffrn_reflns_theta_min         4.453
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.689
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58282
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.131
_refine_diff_density_min         -0.140
_refine_diff_density_rms         0.030
_refine_ls_abs_structure_details
;
 Flack x determined using 1591 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         4292
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0602P)^2^+0.1268P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1010
_refine_ls_wR_factor_ref         0.1025
_reflns_Friedel_coverage         0.716
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                4025
_reflns_number_total             4292
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02079c2.cif
_cod_data_source_block           zhangzhangsheng_0302
_cod_depositor_comments
;
Adding full bibliography for 1567165--1567169.cif.

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C28 H24 O4'
_cod_original_formula_weight         424.47
_cod_original_formula_moiety         '2(C14 H12 O2)'
_cod_original_formula_units_Z            4
_cod_database_code               1567168
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C00A(H00G), C00K(H00K)
1.b Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00C), C00Q(H00Q,H00R), C00R(H00D,H00F), C00T(H00T,H00V)
1.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00H), C00E(H00E), C00G(H00I), C00I(H00J), C00L(H00L),
 C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P), C00S(H00S), C00U(H00U),
 C00V(H00W), C00W(H00X)
;
_shelx_res_checksum              88974
_shelx_hkl_checksum              51242
_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 1.627
_oxdiff_exptl_absorpt_empirical_full_min 0.549