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_1572257
_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         'C33 H38 N2 O'
_chemical_formula_sum            'C33 H38 N2 O'
_chemical_formula_weight         478.65
_chemical_name_systematic
(S)-(2,3,4,5,6-pentamethylphenyl)(2-phenyl-3-(4-phenylpiperazin-1-yl)cyclopent-1-en-1-yl)methanone
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-30
_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                 99.616(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8634(3)
_cell_length_b                   23.6728(7)
_cell_length_c                   8.7931(3)
_cell_measurement_reflns_used    25113
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      68.3140
_cell_measurement_theta_min      3.4600
_cell_volume                     2639.99(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (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 n/a (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.990
_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     17.00 109.00   0.50    0.42    --   41.33  68.00-160.00  184
  2  \w    -26.00  66.00   0.50    0.42    --   41.33 -68.00  66.00  184
  3  \w    -83.00 -14.00   0.50    2.00    --  -82.50  68.00-160.00  138
  4  \w   -150.00 -58.00   0.50    2.00    --  -82.50 -68.00  66.00  184
  5  \w     29.00  83.00   0.50    2.00    --   96.67 -68.00  66.00  108
  6  \w     73.00 165.00   0.50    2.00    --   96.67  68.00-160.00  184
  7  \w    -37.00  27.00   0.50    0.42    --  -41.33  32.00  30.00  128
  8  \w   -109.00 -17.00   0.50    0.42    --  -41.33 -68.00  66.00  184
  9  \w    -28.00  30.00   0.50    0.42    --  -41.33  21.00 -60.00  116
 10  \w    -28.00  30.00   0.50    0.42    --  -41.33  21.00  30.00  116
 11  \w    -28.00  30.00   0.50    0.42    --  -41.33  21.00 -30.00  116
 12  \w    -65.00  27.00   0.50    0.42    --  -41.33  68.00-160.00  184
 13  \w     18.00  80.00   0.50    0.42    --   41.33-104.00 150.00  124
 14  \w    -30.00  28.00   0.50    0.42    --   41.33 -21.00  60.00  116
 15  \w    -34.00  24.00   0.50    0.42    --   41.33 -11.00-120.00  116
 16  \w   -101.00 -23.00   0.50    2.00    --  -82.50 145.00-150.00  156
 17  \w    -47.00 -15.00   0.50    2.00    --  -82.50  42.00-150.00   64
 18  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00-120.00   54
 19  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00 150.00   54
 20  \w     30.00 109.00   0.50    2.00    --   96.67-117.00  90.00  158
 21  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00  90.00   54
 22  \w     29.00  68.00   0.50    2.00    --   96.67 -59.00 -60.00   78
 23  \w     99.00 164.00   0.50    2.00    --   96.67 117.00 150.00  130
 24  \w     73.00 165.00   0.50    2.00    --   96.67  68.00 150.00  184
 25  \w     82.00 167.00   0.50    2.00    --   96.67  25.00 150.00  170
 26  \w     73.00 165.00   0.50    2.00    --   96.67  68.00-180.00  184
 27  \w     29.00  83.00   0.50    2.00    --   96.67 -68.00  90.00  108
 28  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00 -60.00   54
 29  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00 120.00   54
 30  \w     29.00  68.00   0.50    2.00    --   96.67 -59.00 120.00   78
 31  \w     75.00 164.00   0.50    2.00    --   96.67  59.00  90.00  178
 32  \w     83.00 164.00   0.50    2.00    --   96.67  33.00 -60.00  162
 33  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00   0.00   54
 34  \w     22.00 106.00   0.50    2.00    --   96.67 -96.00 -90.00  168
 35  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00 -90.00   54
 36  \w   -109.00 -18.00   0.50    0.42    --  -41.33 -65.00   0.00  182
 37  \w   -110.00 -14.00   0.50    0.42    --  -41.33 -77.00 -90.00  192
 38  \w   -110.00 -14.00   0.50    0.42    --  -41.33 -77.00 -30.00  192
 39  \w    -79.00   4.00   0.50    0.42    --  -41.33 104.00-150.00  166
 40  \w     18.00  80.00   0.50    0.42    --   41.33-104.00  30.00  124
 41  \w     18.00 109.00   0.50    0.42    --   41.33  65.00 150.00  182
 42  \w     15.00 110.00   0.50    0.42    --   41.33  77.00-150.00  190
 43  \w     18.00 109.00   0.50    0.42    --   41.33  65.00   0.00  182
 44  \w     15.00 110.00   0.50    0.42    --   41.33  77.00  90.00  190
 45  \w     18.00 109.00   0.50    0.42    --   41.33  65.00 -90.00  182
 46  \w   -151.00 -55.00   0.50    2.00    --  -82.50 -77.00 -30.00  192
 47  \w   -151.00 -55.00   0.50    2.00    --  -82.50 -77.00 120.00  192
 48  \w   -151.00 -55.00   0.50    2.00    --  -82.50 -77.00   0.00  192
 49  \w   -151.00 -55.00   0.50    2.00    --  -82.50 -77.00 -90.00  192
 50  \w     30.00 109.00   0.50    2.00    --   96.67-117.00-120.00  158
 51  \w     75.00 164.00   0.50    2.00    --   96.67  59.00  30.00  178
 52  \w     30.00  57.00   0.50    2.00    --   96.67 -50.00-180.00   54
 53  \w     44.00  70.00   0.50    2.00    --   96.67-145.00-120.00   52
 54  \w     80.00 163.00   0.50    2.00    --   96.67  42.00   0.00  166
 55  \w     29.00  83.00   0.50    2.00    --   96.67 -68.00 -90.00  108
 56  \w     75.00 164.00   0.50    2.00    --   96.67  59.00-120.00  178
 57  \w     30.00 109.00   0.50    2.00    --   96.67-117.00  30.00  158
 58  \w     75.00 164.00   0.50    2.00    --   96.67  59.00  60.00  178
 59  \w     70.00 165.00   0.50    2.00    --   96.67  77.00 -60.00  190
;
_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      0.1026369000
_diffrn_orient_matrix_UB_12      0.0342258000
_diffrn_orient_matrix_UB_13      0.0077287000
_diffrn_orient_matrix_UB_21      0.0319628000
_diffrn_orient_matrix_UB_22      -0.0369825000
_diffrn_orient_matrix_UB_23      -0.1286762000
_diffrn_orient_matrix_UB_31      -0.0566725000
_diffrn_orient_matrix_UB_32      0.0411924000
_diffrn_orient_matrix_UB_33      -0.1222340000
_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  0.0752
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            37941
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.424
_diffrn_reflns_theta_min         3.485
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.552
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45257
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic reddish red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.204
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_preparation       'crystallised from DCM'
_exptl_crystal_recrystallization_method 'not needed'
_exptl_crystal_size_max          0.002
_exptl_crystal_size_mid          0.002
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.562
_refine_diff_density_min         -0.195
_refine_diff_density_rms         0.041
_refine_ls_extinction_coef       0.00145(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     331
_refine_ls_number_reflns         4821
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0492P)^2^+1.2661P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1164
_refine_ls_wR_factor_ref         0.1222
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4252
_reflns_number_total             4821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02842b2.cif
_cod_data_source_block           ksk-kc93_auto
_cod_depositor_comments
'Adding full bibliography for 1572257--1572260.cif.'
_cod_database_code               1572257
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     100K
_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:
 C20(H20)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18a,H18b), C19(H19a,H19b), C15(H15a,H15b), C16(H16a,H16b), C24(H24a,
 H24b), C23(H23a,H23b)
2.c Aromatic/amide H refined with riding coordinates:
 C36(H36), C32(H32), C35(H35), C30(H30), C34(H34), C26(H26), C29(H29),
 C33(H33), C28(H28), C27(H27)
2.d Idealised Me refined as rotating group:
 C11(H11a,H11b,H11c), C12(H12a,H12b,H12c), C9(H9a,H9b,H9c), C10(H10a,H10b,
 H10c), C13(H13a,H13b,H13c)
;
_shelx_res_checksum              24287
_shelx_hkl_checksum              32149
_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 1.756
_oxdiff_exptl_absorpt_empirical_full_min 0.607