Regioselective ring-opening of epoxides towards Markovnikov alcohols: a metal-free catalytic approach using abnormal N-heterocyclic carbene
P., Sreejyothi; Sarkar, Pallavi; Dutta, Supriti; Das, Arpan; Pati, Swapan K.; Mandal, Swadhin K.; Chemical Communications  (2022) –; doi:10.1039/D2CC03549A

data_7130483
_publ_section_title
;
 Regioselective ring-opening of epoxides towards Markovnikov alcohols: a
 metal-free catalytic approach using abnormal N-heterocyclic carbene
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03549A
_journal_year                    2022
_chemical_formula_moiety         'C66 H53 B Cl F15 N2 O2'
_chemical_formula_sum            'C66 H53 B Cl F15 N2 O2'
_chemical_formula_weight         1237.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-19 deposited with the CCDC.	2022-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.1380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.88130(10)
_cell_length_b                   15.85180(10)
_cell_length_c                   26.0785(2)
_cell_measurement_reflns_used    41423
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.0640
_cell_measurement_theta_min      2.8190
_cell_volume                     7317.53(9)
_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 1.3 (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(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 0.994
_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    -65.00  26.00   0.50    0.75    --  -41.33  65.00-150.00  182
  2  \w   -109.00 -18.00   0.50    0.75    --  -41.33 -65.00  73.00  182
  3  \w    -26.00  65.00   0.50    0.75    --   41.33 -65.00  73.00  182
  4  \w     18.00 109.00   0.50    0.75    --   41.33  65.00-150.00  182
  5  \w    -78.00 -15.00   0.50    3.50    --  -82.50  65.00-150.00  126
  6  \w     29.00  78.00   0.50    3.50    --   96.67 -65.00  73.00   98
  7  \w     73.00 164.00   0.50    3.50    --   96.67  65.00-150.00  182
  8  \w    -37.00  27.00   0.50    0.75    --  -41.33  32.00   0.00  128
  9  \w   -109.00 -28.00   0.50    0.75    --  -41.33 -32.00 -90.00  162
 10  \w    -34.00  24.00   0.50    0.75    --   41.33 -11.00 120.00  116
 11  \w     22.00 113.00   0.50    0.75    --   41.33  21.00 -30.00  182
 12  \w     15.00 110.00   0.50    0.75    --   41.33  77.00-180.00  190
 13  \w     41.00 100.00   0.50    0.75    --   41.33-138.00   0.00  118
 14  \w     18.00  80.00   0.50    0.75    --   41.33-104.00 -30.00  124
 15  \w   -157.00 -83.00   0.50    3.50    --  -82.50 -96.00 150.00  148
 16  \w   -150.00 -59.00   0.50    3.50    --  -82.50 -65.00  73.00  182
 17  \w     73.00 165.00   0.50    3.50    --   96.67  68.00-180.00  184
 18  \w     29.00  68.00   0.50    3.50    --   96.67 -59.00   0.00   78
 19  \w     27.00 127.00   0.50    3.50    --   96.67 -87.00  60.00  200
 20  \w     30.00  57.00   0.50    3.50    --   96.67 -50.00 120.00   54
 21  \w    105.00 170.00   0.50    3.50    --   96.67  96.00 -60.00  130
 22  \w     83.00 164.00   0.50    3.50    --   96.67  33.00 -60.00  162
 23  \w     30.00  57.00   0.50    3.50    --   96.67 -50.00 -30.00   54
 24  \w     99.00 164.00   0.50    3.50    --   96.67 117.00-120.00  130
 25  \w     30.00  57.00   0.50    3.50    --   96.67 -50.00 150.00   54
 26  \w     99.00 164.00   0.50    3.50    --   96.67 117.00 -90.00  130
 27  \w     22.00 106.00   0.50    3.50    --   96.67 -96.00 -90.00  168
 28  \w     29.00  68.00   0.50    3.50    --   96.67 -59.00 -90.00   78
 29  \w     30.00  57.00   0.50    3.50    --   96.67 -50.00  30.00   54
 30  \w     30.00  57.00   0.50    3.50    --   96.67 -50.00 -60.00   54
 31  \w     83.00 164.00   0.50    3.50    --   96.67  33.00 -30.00  162
 32  \w     30.00 109.00   0.50    3.50    --   96.67-117.00 120.00  158
 33  \w    105.00 170.00   0.50    3.50    --   96.67  96.00  90.00  130
 34  \w     44.00 127.00   0.50    3.50    --   96.67-145.00 -60.00  166
 35  \w   -110.00 -14.00   0.50    0.75    --  -41.33 -77.00  30.00  192
 36  \w   -110.00 -14.00   0.50    0.75    --  -41.33 -77.00-120.00  192
 37  \w    -61.00  26.00   0.50    0.75    --  -41.33  54.00  90.00  174
 38  \w   -110.00 -14.00   0.50    0.75    --  -41.33 -77.00-180.00  192
 39  \w   -110.00 -14.00   0.50    0.75    --  -41.33 -77.00 -60.00  192
 40  \w    -37.00  27.00   0.50    0.75    --  -41.33  32.00 -60.00  128
 41  \w     15.00 110.00   0.50    0.75    --   41.33  77.00  60.00  190
 42  \w     15.00 110.00   0.50    0.75    --   41.33  77.00 120.00  190
 43  \w    -30.00  28.00   0.50    0.75    --   41.33 -21.00 -30.00  116
 44  \w     28.00 109.00   0.50    0.75    --   41.33  32.00-180.00  162
 45  \w     15.00 110.00   0.50    0.75    --   41.33  77.00   0.00  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      -0.0369809000
_diffrn_orient_matrix_UB_12      -0.0572739000
_diffrn_orient_matrix_UB_13      0.0369828000
_diffrn_orient_matrix_UB_21      -0.0762639000
_diffrn_orient_matrix_UB_22      0.0445863000
_diffrn_orient_matrix_UB_23      -0.0161825000
_diffrn_orient_matrix_UB_31      -0.0198066000
_diffrn_orient_matrix_UB_32      -0.0646475000
_diffrn_orient_matrix_UB_33      -0.0439327000
_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  0.0408
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            79533
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.236
_diffrn_reflns_theta_min         3.221
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.130
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78968
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.123
_exptl_crystal_description       block
_exptl_crystal_F_000             2544
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.432
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.00032(3)
_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   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     793
_refine_ls_number_reflns         13311
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0494
_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^)+(0.0601P)^2^+6.0617P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1314
_refine_ls_wR_factor_ref         0.1346
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11756
_reflns_number_total             13311
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03549a2.cif
_cod_data_source_block           sree_anhcbcf_auto
_cod_database_code               7130483
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N B F O Cl'
_chemical_oxdiff_usercomment     '100 K'
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.849
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C5(H5), C19(H19), C22(H22), C37(H37), C40(H40)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12), C15(H15), C16(H16), C17(H17), C26(H26),
 C27(H27), C28(H28), C29(H29), C30(H30), C33(H33), C34(H34), C35(H35), C44(H44),
  C45(H45), C46(H46), C47(H47), C48(H48)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 550 electrons were 
found in a volume of 2077\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3.5[C4H8O] per Asymmetric Unit 
which account for 560 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              74365
_shelx_hkl_checksum              95591
_shelx_fab_checksum              64819
_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 1.922
_oxdiff_exptl_absorpt_empirical_full_min 0.672