One-pot Synthesis of Multi-substituted Conjugated Dienones by Trapping Allene Carbocation with Active Ylides
Ni, Dan; Song, Longlong; Zhao, Yun; Liu, Shunying; Chemical Communications  (2022) –; doi:10.1039/D1CC06405C

data_7129547
_publ_section_title
;
 One-pot Synthesis of Multi-substituted Conjugated Dienones by Trapping
 Allene Carbocation with Active Ylides
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06405C
_journal_year                    2022
_chemical_formula_moiety
'0.5(C33 H28 F3 N2 O2 S), 0.5(C33 H30 F3 N2 O2 S)'
_chemical_formula_sum            'C33 H29 F3 N2 O2 S'
_chemical_formula_weight         574.64
_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             2021-09-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-09-20 deposited with the CCDC.	2022-01-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.234(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.6154(10)
_cell_length_b                   11.0222(3)
_cell_length_c                   25.2859(12)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      73.1400
_cell_measurement_theta_min      3.1880
_cell_volume                     5951.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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     42.00  68.00   1.00    2.00    --    0.00  37.00 120.00   26
  2  \w    -12.00  16.00   1.00    2.00    --    0.00 -37.00 120.00   28
  3  \w    -89.00 -27.00   1.00    2.00    --    0.00 -37.00 120.00   62
  4  \w    -88.00   8.00   1.00    2.00    --    0.00 -37.00-150.00   96
  5  \w    -86.00 -30.00   1.00    2.00    --    0.00 -57.00 -60.00   56
  6  \w    -39.00  17.00   1.00    2.00    --    0.00 -37.00 -30.00   56
  7  \w      9.00  39.00   1.00    4.00    --   95.80 -30.00 -60.00   30
  8  \w      6.00 102.00   1.00    4.00    --   95.80 -82.00  30.00   96
  9  \w     31.00 128.00   1.00    4.00    --   95.80 -82.00-180.00   97
 10  \w     21.00  47.00   1.00    4.00    --   95.80 -82.00 -60.00   26
 11  \w     69.00 121.00   1.00    4.00    --   95.80 -82.00 -60.00   52
 12  \w      6.00  91.00   1.00    4.00    --   95.80 -61.00  90.00   85
 13  \w     76.00 104.00   1.00    4.00    --   95.80 -82.00 -90.00   28
 14  \w      6.00  71.00   1.00    4.00    --   95.80 -15.00-180.00   65
 15  \w      6.00 120.00   1.00    4.00    --   95.80 -61.00-180.00  114
 16  \w      9.00 115.00   1.00    4.00    --   95.80 -45.00 -90.00  106
 17  \w     28.00 111.00   1.00    4.00    --   95.80 -82.00  90.00   83
 18  \w     77.00 123.00   1.00    4.00    --   95.80 -15.00-180.00   46
 19  \w     46.00 106.00   1.00    4.00    --   95.80 -30.00 -60.00   60
 20  \w     12.00  37.00   1.00    4.00    --   95.80 -82.00 150.00   25
 21  \w     78.00 103.00   1.00    4.00    --   95.80 -82.00 150.00   25
 22  \w     54.00 132.00   1.00    4.00    --   95.80   0.00 -60.00   78
 23  \w     40.00 103.00   1.00    4.00    --   95.80 -82.00 -30.00   63
 24  \w    141.00 185.00   1.00    4.00    --   95.80  30.00 -60.00   44
 25  \w     66.00 104.00   1.00    4.00    --   95.80 -82.00   0.00   38
 26  \w    100.00 126.00   1.00    4.00    --   95.80 -82.00  60.00   26
 27  \w      6.00  35.00   1.00    4.00    --   95.80   0.00 -60.00   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0090342000
_diffrn_orient_matrix_UB_12      -0.0583925000
_diffrn_orient_matrix_UB_13      -0.0521754000
_diffrn_orient_matrix_UB_21      0.0538480000
_diffrn_orient_matrix_UB_22      -0.0780199000
_diffrn_orient_matrix_UB_23      0.0379769000
_diffrn_orient_matrix_UB_31      -0.0471704000
_diffrn_orient_matrix_UB_32      -0.1001304000
_diffrn_orient_matrix_UB_33      0.0008507000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0902
_diffrn_reflns_av_unetI/netI     0.0682
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            64000
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.199
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.399
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40015
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.283
_exptl_crystal_description       block
_exptl_crystal_F_000             2400
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.801
_refine_diff_density_min         -0.845
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     747
_refine_ls_number_reflns         10529
_refine_ls_number_restraints     35
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.1468
_refine_ls_R_factor_gt           0.1198
_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^)+(0.0933P)^2^+22.9078P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2791
_refine_ls_wR_factor_ref         0.2966
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7586
_reflns_number_total             10529
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06405c2.cif
_cod_data_source_block           exp_2265
_cod_database_code               7129547
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.884
_shelx_estimated_absorpt_t_min   0.591
_reflns_odcompleteness_completeness 99.95
_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. Shared sites
{S2, C66}
{S3, C67}
3. Rigid bond restraints
 C33, N1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1, C15
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, F1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, F3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C29, F2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C33 \\sim N1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C29 \\sim F1: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C29 \\sim F3: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C29 \\sim F2: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
Uanis(C33) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(S2) = Uanis(C66)
Uanis(S3) = Uanis(C67)
5. Others
 Fixed Sof: S2(0.5) S3(0.5) C66(0.5) C67(0.5)
6.a Ternary CH refined with riding coordinates:
 C46(H46), C27(H27)
6.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B)
6.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C50(H50), C51(H51),
 C53(H53), C54(H54), C56(H56), C57(H57), C59(H59), C60(H60), C2(H2), C3(H3),
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13), C14(H14),
  C15(H15), C21(H21), C22(H22), C24(H24), C25(H25), C28(H28)
6.d Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,
 H64C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C)
;
_shelx_res_checksum              62629
_shelx_hkl_checksum              93304
_shelx_fab_checksum              36753
_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 2.191
_oxdiff_exptl_absorpt_empirical_full_min 0.355