Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a combined experimental and computational investigation.
Sarkar, Koushik; Behera, Prativa; Roy, Lisa; Maji, Biplab; Chemical science 15 (2024) 14287–14294; doi:10.1039/d4sc02842b

data_1572259
_publ_section_title
;
 Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a
 combined experimental and computational investigation.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              14287
_journal_page_last               14294
_journal_paper_doi               10.1039/d4sc02842b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C23 H26 O'
_chemical_formula_sum            'C23 H26 O'
_chemical_formula_weight         318.44
_chemical_name_systematic
(2,3,4,5,6-pentamethylphenyl)(2-phenylcyclopent-1-en-1-yl)methanone
_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     iterative
_audit_creation_date             2023-01-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-01-20 deposited with the CCDC.	2024-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.03845(7)
_cell_length_b                   13.58231(12)
_cell_length_c                   16.53779(14)
_cell_measurement_reflns_used    21321
_cell_measurement_temperature    100.4(9)
_cell_measurement_theta_max      68.0490
_cell_measurement_theta_min      2.6570
_cell_volume                     1805.61(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.4(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -30.00  31.00   0.50    0.20    --   40.33 -25.00 -90.00  122
  2  \w    105.00 170.00   0.50    0.20    --   96.67  96.00 -30.00  130
  3  \w    -35.00  24.00   0.50    0.20    --   40.33 -12.00  30.00  118
  4  \w    -27.00  62.00   0.50    0.20    --   40.33 -60.00   4.00  178
  5  \w    -27.00  64.00   0.50    0.20    --   40.33 -64.00 -90.00  182
  6  \w     30.00  57.00   0.50    0.20    --   96.67 -50.00 -90.00   54
  7  \w     29.00  83.00   0.50    0.20    --   96.67 -68.00 -90.00  108
  8  \w     29.00  83.00   0.50    0.20    --   96.67 -68.00-120.00  108
  9  \w     30.00  57.00   0.50    0.20    --   96.67 -50.00-150.00   54
 10  \w     29.00  83.00   0.50    0.20    --   96.67 -68.00   0.00  108
 11  \w     29.00  70.00   0.50    0.20    --   96.67 -60.00   4.00   82
 12  \w     28.00 105.00   0.50    0.20    --   96.67 -77.00 120.00  154
 13  \w     30.00  57.00   0.50    0.20    --   96.67 -50.00 120.00   54
 14  \w     30.00  57.00   0.50    0.20    --   96.67 -50.00  90.00   54
 15  \w     29.00  68.00   0.50    0.20    --   96.67 -59.00  60.00   78
 16  \w     27.00 127.00   0.50    0.20    --   96.67 -87.00   0.00  200
 17  \w     44.00 127.00   0.50    0.20    --   96.67-145.00 -30.00  166
 18  \w     30.00 109.00   0.50    0.20    --   96.67-117.00-120.00  158
 19  \w     44.00 127.00   0.50    0.20    --   96.67-145.00-120.00  166
 20  \w     30.00 109.00   0.50    0.20    --   96.67-117.00 -30.00  158
 21  \w     44.00 127.00   0.50    0.20    --   96.67-145.00  90.00  166
 22  \w     30.00 109.00   0.50    0.20    --   96.67-117.00  90.00  158
 23  \w     30.00 109.00   0.50    0.20    --   96.67-117.00  30.00  158
 24  \w     22.00 106.00   0.50    0.20    --   96.67 -96.00  90.00  168
 25  \w     30.00 109.00   0.50    0.20    --   96.67-117.00   0.00  158
 26  \w     22.00 106.00   0.50    0.20    --   96.67 -96.00-120.00  168
 27  \w     18.00  79.00   0.50    0.20    --   40.33-104.00-180.00  122
 28  \w     41.00  99.00   0.50    0.20    --   40.33-138.00  30.00  116
 29  \w     18.00  79.00   0.50    0.20    --   40.33-104.00-120.00  122
 30  \w    -70.00 -14.00   0.50    0.20    --  -82.50  60.00 144.00  112
 31  \w    -47.00 -15.00   0.50    0.20    --  -82.50  42.00  30.00   64
 32  \w    -47.00 -15.00   0.50    0.20    --  -82.50  42.00 -30.00   64
 33  \w    -47.00 -15.00   0.50    0.20    --  -82.50  42.00-150.00   64
 34  \w    -63.00  27.00   0.50    0.20    --  -40.33  64.00-120.00  180
 35  \w    -24.00  35.00   0.50    0.20    --  -40.33  12.00 -90.00  118
 36  \w    -31.00  30.00   0.50    0.20    --  -40.33  25.00 -30.00  122
 37  \w    -62.00  28.00   0.50    0.20    --  -40.33  60.00 144.00  180
 38  \w   -108.00 -17.00   0.50    0.20    --  -40.33 -64.00 -60.00  182
 39  \w   -107.00 -18.00   0.50    0.20    --  -40.33 -60.00   4.00  178
 40  \w   -151.00 -61.00   0.50    0.20    --  -82.50 -59.00  60.00  180
 41  \w   -151.00 -60.00   0.50    0.20    --  -82.50 -60.00   4.00  182
 42  \w   -107.00 -21.00   0.50    0.20    --  -40.33 -50.00-150.00  172
 43  \w     12.00  43.00   0.50    0.20    --   40.33  81.00 -71.28   62
 44  \w      8.00  35.00   0.50    0.20    --   40.33  93.00-140.12   54
 45  \w      9.00  43.00   0.50    0.20    --   40.33  89.00-147.79   68
 46  \w      9.00  43.00   0.50    0.20    --   40.33  89.00  11.52   68
 47  \w     11.00  43.00   0.50    0.20    --   40.33  84.00  42.67   64
 48  \w      8.00  35.00   0.50    0.20    --   40.33  93.00  82.87   54
 49  \w     13.00  43.00   0.50    0.20    --   40.33  79.00 177.69   60
 50  \w     19.00 108.00   0.50    0.20    --   40.33  60.00 144.00  178
 51  \w     14.00 109.00   0.50    0.20    --   40.33  77.00  90.00  190
 52  \w     14.00 109.00   0.50    0.20    --   40.33  77.00 -60.00  190
 53  \w     21.00 107.00   0.50    0.20    --   40.33  50.00-150.00  172
 54  \w     73.00 165.00   0.50    0.20    --   96.67  68.00   0.00  184
 55  \w     83.00 164.00   0.50    0.20    --   96.67  33.00 -90.00  162
 56  \w     83.00 164.00   0.50    0.20    --   96.67  33.00-120.00  162
 57  \w     82.00 167.00   0.50    0.20    --   96.67  25.00  60.00  170
 58  \w     78.00 163.00   0.50    0.20    --   96.67  50.00  90.00  170
 59  \w     75.00 164.00   0.50    0.20    --   96.67  60.00 144.00  178
 60  \w     78.00 163.00   0.50    0.20    --   96.67  50.00 120.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1164594000
_diffrn_orient_matrix_UB_12      0.0876756000
_diffrn_orient_matrix_UB_13      0.0168923000
_diffrn_orient_matrix_UB_21      0.1233601000
_diffrn_orient_matrix_UB_22      0.0392009000
_diffrn_orient_matrix_UB_23      0.0636289000
_diffrn_orient_matrix_UB_31      0.0892055000
_diffrn_orient_matrix_UB_32      0.0603198000
_diffrn_orient_matrix_UB_33      -0.0659055000
_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  0.0987
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26187
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.190
_diffrn_reflns_theta_min         4.212
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.529
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33585
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.171
_exptl_crystal_description       block
_exptl_crystal_F_000             688
_exptl_crystal_preparation       'Crystallised by  Hexane in dichloromethane'
_exptl_crystal_recrystallization_method
'Dissolved in DCM and dropwise added in hexane'
_exptl_crystal_size_max          0.002
_exptl_crystal_size_mid          0.002
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1338 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(17)
_refine_ls_extinction_coef       0.0037(6)
_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   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     223
_refine_ls_number_reflns         3295
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0361
_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^)+(0.0598P)^2^+0.3344P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0965
_refine_ls_wR_factor_ref         0.0970
_reflns_Friedel_coverage         0.731
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3224
_reflns_number_total             3295
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02842b2.cif
_cod_data_source_block           bipkskkc145-2_auto
_cod_depositor_comments
'Adding full bibliography for 1572257--1572260.cif.'
_cod_database_code               1572259
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C O H'
_chemical_oxdiff_usercomment     100K
_shelx_estimated_absorpt_t_max   0.999
_shelx_estimated_absorpt_t_min   0.999
_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 Secondary CH2 refined with riding coordinates:
 C22(H22a,H22b), C23(H23a,H23b), C24(H24a,H24b)
2.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C18(H18), C17(H17), C16(H16), C19(H19)
2.c Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c), C13(H13a,H13b,H13c), C9(H9a,H9b,H9c), C12(H12a,H12b,
 H12c), C11(H11a,H11b,H11c)
;
_shelx_res_checksum              63306
_shelx_hkl_checksum              69728
_olex2_exptl_crystal_mounting_method Yes
_olex2_submission_original_sample_id KSK_KC145B2
_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 1.873
_oxdiff_exptl_absorpt_empirical_full_min 0.388