Rhodium-Catalyzed Tetradehydro-Diels–Alder Reactions of Enediynes via a Rhodium-stabilized Cyclic Allene
Thadkapally, Srinivas; Farshadfar, Kaveh; Drew, Melanie; Richardson, Christopher; Ariafard, Alireza; Pyne, Stephen G.; Hyland, Christopher James Timothy; Chemical Science  (2020) –; doi:10.1039/D0SC04390G

data_1558990
_publ_section_title
;
 Rhodium-Catalyzed Tetradehydro-Diels--Alder Reactions of Enediynes via a
 Rhodium-stabilized Cyclic Allene
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04390G
_journal_year                    2020
_chemical_formula_moiety         'C22 H21 N O2 S'
_chemical_formula_sum            'C22 H21 N O2 S'
_chemical_formula_weight         363.46
_chemical_name_systematic
(rac)-1-methyl-5-phenyl-2-(p-tolylsulfinyl)isoindoline
_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             2019-12-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-04-28 deposited with the CCDC.	2020-09-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.247(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.9149(2)
_cell_length_b                   7.8607(2)
_cell_length_c                   34.1007(12)
_cell_measurement_reflns_used    11472
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      30.5530
_cell_measurement_theta_min      2.3710
_cell_volume                     1845.81(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_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      149.99(10)
_diffrn_detector                 'HyPix Bantam HPC'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -74.00 110.00   0.50   20.00    --   20.00  54.00  36.51  368
  2  \w    -74.00 109.50   0.50   20.00    --   20.00  54.00 -60.00  367
  3  \w    -71.00 -10.00   0.50   20.00    --   20.00  54.00  98.22  122
  4  \w     41.00 110.00   0.50   20.00    --   20.00  54.00  98.22  138
  5  \w    -72.00  91.00   0.50   20.00    --   20.00  54.00 148.05  326
  6  \w    -73.00  13.00   0.50   20.00    --   20.00  54.00   0.00  172
  7  \w     22.00 108.00   0.50   20.00    --   20.00  54.00   0.00  172
  8  \w    -67.00 -29.00   0.50   20.00    --   20.00  54.00  69.25   76
  9  \w    -74.00  64.50   0.50   20.00    --   20.00  54.00 -37.99  277
 10  \w    -15.00  39.00   0.50   20.00    --   20.00  54.00  64.79  108
 11  \w    -74.00  71.00   0.50   20.00    --   20.00  54.00 -90.00  290
 12  \w    -74.00 -40.00   0.50   20.00    --   20.00  54.00  30.00   68
 13  \w    -70.00 -23.00   0.50   20.00    --   20.00  54.00 120.00   94
 14  \w    -73.00  78.00   0.50   20.00    --   20.00  54.00-165.84  302
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0737498000
_diffrn_orient_matrix_UB_12      0.0624335000
_diffrn_orient_matrix_UB_13      -0.0015769000
_diffrn_orient_matrix_UB_21      0.0092472000
_diffrn_orient_matrix_UB_22      0.0096605000
_diffrn_orient_matrix_UB_23      0.0206712000
_diffrn_orient_matrix_UB_31      0.0707619000
_diffrn_orient_matrix_UB_32      0.0638977000
_diffrn_orient_matrix_UB_33      -0.0015665000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            38229
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.572
_diffrn_reflns_theta_min         2.399
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.191
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94950
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.15 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_description       plate
_exptl_crystal_F_000             768
_exptl_crystal_recrystallization_method DCM/MeOH
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         5180
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0429
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0481P)^2^+0.6484P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1054
_refine_ls_wR_factor_ref         0.1116
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4159
_reflns_number_total             5180
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04390g2.cif
_cod_data_source_block           exp_130_sri
_cod_original_cell_volume        1845.81(11)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               1558990
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C22 H21 N O2 S'
_chemical_oxdiff_usercomment     Srinivas
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.927
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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, All C(H,H,H,H,H,H) groups
2. Others
 Sof(H7PD)=Sof(H7PE)=Sof(H7PF)=1-FVAR(1)
 Sof(H7PA)=Sof(H7PB)=Sof(H7PC)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C2'(H2'), C3'(H3'), C4'(H4'), C5'(H5'), C6'(H6'),
 C2PP(H2PP), C3PP(H3PP), C5PP(H5PP), C6PP(H6PP)
3.d Idealised Me refined as rotating group:
 C1ME(H1MA,H1MB,H1MC), C7PP(H7PA,H7PB,H7PC), C7PP(H7PD,H7PE,H7PF)
;
_shelx_res_checksum              64434
_olex2_exptl_crystal_mounting_method 'Mitegen mount and Paratone'
_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 1.235
_oxdiff_exptl_absorpt_empirical_full_min 0.932