Palladium-catalyzed asymmetric [4 + 3] cycloaddition of methylene-trimethylenemethane: access to seven-membered exocyclic axially chiral allenes.
Wu, Yafei; Wang, Zhuo; Shan, Yuqian; Ma, Yukun; Li, Teng; Yuan, Chunhao; Guo, Hongchao; Mao, Biming; Chemical science 15 (2024) 9703–9708; doi:10.1039/d4sc01649a

data_1571670
_publ_section_title
;
 Palladium-catalyzed asymmetric [4 + 3] cycloaddition of
 methylene-trimethylenemethane: access to seven-membered exocyclic axially
 chiral allenes.
;
_journal_issue                   25
_journal_name_full               'Chemical science'
_journal_page_first              9703
_journal_page_last               9708
_journal_paper_doi               10.1039/d4sc01649a
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H23 N O3 S'
_chemical_formula_sum            'C23 H23 N O3 S'
_chemical_formula_weight         393.48
_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             2023-11-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-25 deposited with the CCDC.	2024-05-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.79420(10)
_cell_length_b                   10.27180(10)
_cell_length_c                   25.9536(4)
_cell_measurement_reflns_used    9819
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.1870
_cell_measurement_theta_min      1.7110
_cell_volume                     2077.86(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.89a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.89a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_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     69.00  95.00   0.50    0.51    --   42.30  82.00 -90.00   52
  2  \w     21.00  72.00   0.50    0.51    --   42.30 -43.00   0.00  102
  3  \w     37.00  67.00   0.50    0.51    --   42.30 -82.00   0.00   60
  4  \w    100.00 131.00   0.50    0.51    --   42.30  82.00 -90.00   62
  5  \w    -47.00 -22.00   0.50    0.51    --   42.30 -82.00-180.00   50
  6  \w     42.00  72.00   0.50    0.51    --   42.30 -54.00-120.00   60
  7  \w     34.00  67.00   0.50    0.51    --   42.30 -82.00  90.00   66
  8  \w     12.00  67.00   0.50    0.51    --   42.30 -77.00   0.00  110
  9  \w     72.00 129.00   0.50    0.51    --   42.30  54.00  30.00  114
 10  \w     19.00  70.00   0.50    0.51    --   42.30 -82.00 -90.00  102
 11  \w     31.00  57.00   0.50    0.51    --   42.30  82.00 -90.00   52
 12  \w     35.00  69.00   0.50    0.51    --   42.30 -82.00-180.00   68
 13  \w    -45.00  13.00   0.50    0.51    --   42.30 -77.00 120.00  116
 14  \w     28.00  61.00   0.50    0.51    --   42.30 -77.00 120.00   66
 15  \w     14.00 126.00   0.50    0.51    --   42.30  54.00-180.00  224
 16  \w    -47.00  -8.00   0.50    0.51    --   42.30 -43.00   0.00   78
 17  \w    -22.00  51.00   0.50    0.51    --   42.30 -65.00-120.00  146
 18  \w    -28.00  -2.00   0.50    0.51    --   42.30 -77.00   0.00   52
 19  \w     42.00  67.00   0.50    0.51    --   42.30 -65.00 120.00   50
 20  \w    -34.00  -9.00   0.50    0.51    --   42.30 -65.00 120.00   50
 21  \w     32.00  57.00   0.50    0.51    --   42.30  54.00  30.00   50
 22  \w     71.00  96.00   0.50    0.51    --   42.30  65.00 -60.00   50
 23  \w     -4.00  21.00   0.50    0.51    --   42.30 -54.00-120.00   50
 24  \w     37.00  93.00   0.50    0.50    --   93.70 -82.00  90.00  112
 25  \w    149.00 183.00   0.50    0.50    --   93.70   8.00 150.00   68
 26  \w     81.00 183.00   0.50    0.50    --   93.70  42.00  60.00  204
 27  \w      8.00 110.00   0.50    0.50    --   93.70 -59.00 120.00  204
 28  \w     86.00 112.00   0.50    0.50    --   93.70 -82.00 150.00   52
 29  \w     83.00 146.00   0.50    0.50    --   93.70   8.00 150.00  126
 30  \w      4.00 111.00   0.50    0.50    --   93.70 -59.00 -30.00  214
 31  \w     71.00  97.00   0.50    0.50    --   93.70 -82.00   0.00   52
 32  \w     23.00  97.00   0.50    0.50    --   93.70 -82.00 -30.00  148
 33  \w     72.00  98.00   0.50    0.50    --   93.70 -82.00 -60.00   52
 34  \w      6.00 103.00   0.50    0.50    --   93.70 -82.00-120.00  194
 35  \w     68.00 116.00   0.50    0.50    --   93.70  50.00  90.00   96
 36  \w     15.00  64.00   0.50    0.50    --   93.70 -82.00 -60.00   98
 37  \w      4.00  52.00   0.50    0.50    --   93.70   8.00 150.00   96
 38  \w     98.00 126.00   0.50    0.50    --   93.70 -33.00 120.00   56
 39  \w     75.00 102.00   0.50    0.50    --   93.70 -82.00  30.00   54
 40  \w    157.00 183.00   0.50    0.50    --   93.70  33.00  30.00   52
 41  \w    143.00 169.00   0.50    0.50    --   93.70  50.00  90.00   52
 42  \w     65.00  92.00   0.50    0.50    --   93.70 -82.00-150.00   54
 43  \w     28.00  61.00   0.50    0.50    --   93.70 -82.00 -90.00   66
 44  \w     66.00  91.00   0.50    0.50    --   93.70 -82.00 -90.00   50
 45  \w     93.00 118.00   0.50    0.50    --   93.70  33.00  30.00   50
 46  \w     12.00  72.00   0.50    0.50    --   93.70 -33.00 120.00  120
 47  \w     11.00 105.00   0.50    0.50    --   93.70 -82.00 120.00  188
 48  \w      5.00  38.00   0.50    0.50    --   93.70 -82.00  30.00   66
 49  \w     67.00 105.00   0.50    0.50    --   93.70 -82.00-180.00   76
 50  \w      4.00  42.00   0.50    0.50    --   93.70 -42.00-180.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1902327000
_diffrn_orient_matrix_UB_12      0.0403254000
_diffrn_orient_matrix_UB_13      -0.0018283000
_diffrn_orient_matrix_UB_21      -0.0487457000
_diffrn_orient_matrix_UB_22      -0.1236357000
_diffrn_orient_matrix_UB_23      0.0302544000
_diffrn_orient_matrix_UB_31      0.0220585000
_diffrn_orient_matrix_UB_32      0.0747855000
_diffrn_orient_matrix_UB_33      0.0510341000
_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  0.1448
_diffrn_reflns_av_unetI/netI     0.0799
_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       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            18670
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.322
_diffrn_reflns_theta_min         3.406
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.567
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.00814
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.89a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.258
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.453
_refine_diff_density_min         -0.531
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 1021 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(4)
_refine_ls_extinction_coef       0.0065(12)
_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   1.152
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3774
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.152
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0729
_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^)+(0.1125P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1902
_refine_ls_wR_factor_ref         0.1940
_reflns_Friedel_coverage         0.709
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                3327
_reflns_number_total             3774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01649a2.cif
_cod_data_source_block           mbm_auto
_cod_depositor_comments
'Adding full bibliography for 1571669--1571670.cif.'
_cod_database_code               1571670
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.859
_shelx_estimated_absorpt_t_min   0.745
_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:
 C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C5(H5), C20(H20), C15(H15), C19(H19), C21(H21), C7(H7),
 C18(H18), C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C28(H28A,H28B,H28C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              63271
_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 91.214
_oxdiff_exptl_absorpt_empirical_full_min 0.247