Merging π-Acid and Pd Catalysis: Dearomatizing Spirocyclization/Cross-Coupling Cascade Reactions of Alkyne-Tethered Aromatics
Ho, Hon Eong; Stephens, Thomas C.; Payne, Thomas J.; O’Brien, Peter; Taylor, Richard J. K.; Unsworth, William P.; ACS Catalysis 9 (2018) 504–; doi:10.1021/acscatal.8b03861

data_4515474
_publ_section_title
;
 Merging \p-Acid and Pd Catalysis: Dearomatizing
 Spirocyclization/Cross-Coupling Cascade Reactions of Alkyne-Tethered
 Aromatics
;
_journal_issue                   1
_journal_name_full               'ACS Catalysis'
_journal_page_first              504
_journal_paper_doi               10.1021/acscatal.8b03861
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C44 H32 N2 O2, 2(C0.84 H1.67 Cl1.67)'
_chemical_formula_sum            'C45.67 H35.35 Cl3.35 N2 O2'
_chemical_formula_weight         763.06
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.6518(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.38319(10)
_cell_length_b                   26.3138(4)
_cell_length_c                   19.6731(3)
_cell_measurement_reflns_used    5423
_cell_measurement_temperature    110.05(10)
_cell_measurement_theta_max      70.6610
_cell_measurement_theta_min      4.4890
_cell_volume                     3814.33(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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      110.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_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    -21.00  69.00   1.00    7.00    --    0.00  57.00  60.00   90
  2  \w    -21.00  69.00   1.00    7.00    --    0.00  57.00-150.00   90
  3  \w     23.00 111.00   1.00   28.00    --   54.00-125.00   0.00   88
  4  \w     24.00 124.00   1.00   28.00    --   54.00  77.00 150.00  100
  5  \w     23.00 111.00   1.00   28.00    --   54.00-125.00 -60.00   88
  6  \w    -15.00  75.00   1.00   28.00    --   54.00 -57.00-180.00   90
  7  \w     82.00 178.00   1.00   28.00    --  108.00  37.00 120.00   96
  8  \w    100.00 178.00   1.00   28.00    --  108.00 111.00  30.00   78
  9  \w     38.00 138.00   1.00   28.00    --  108.00 -77.00   0.00  100
 10  \w     86.00 178.00   1.00   28.00    --  108.00  50.00 -90.00   92
 11  \w     40.00 130.00   1.00   28.00    --  108.00 -63.00 120.00   90
 12  \w     36.00 113.00   1.00   28.00    --  108.00-111.00  90.00   77
 13  \w    100.00 178.00   1.00   28.00    --  108.00 111.00  90.00   78
 14  \w     57.00 151.00   1.00   28.00    --  108.00 178.00  30.00   94
 15  \w    -26.00  72.00   1.00    7.00    --    0.00  37.00  30.00   98
 16  \w    -69.00  21.00   1.00    7.00    --    0.00 -57.00-120.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0068235000
_diffrn_orient_matrix_UB_12      0.0269770000
_diffrn_orient_matrix_UB_13      -0.0693173000
_diffrn_orient_matrix_UB_21      0.0658509000
_diffrn_orient_matrix_UB_22      0.0490416000
_diffrn_orient_matrix_UB_23      0.0365142000
_diffrn_orient_matrix_UB_31      0.1982506000
_diffrn_orient_matrix_UB_32      -0.0172110000
_diffrn_orient_matrix_UB_33      -0.0044989000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0182
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            10283
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.065
_diffrn_reflns_theta_max         67.065
_diffrn_reflns_theta_min         3.359
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.727
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.618
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       block
_exptl_crystal_F_000             1586
_exptl_crystal_recrystallization_method hexane/DCM/CDCl3
_exptl_crystal_size_max          0.351
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.438
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         3408
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0490
_refine_ls_R_factor_gt           0.0450
_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^)+(0.0578P)^2^+4.6877P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1154
_refine_ls_wR_factor_ref         0.1189
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3106
_reflns_number_total             3408
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b03861_si_002.cif
_cod_data_source_block           wpu1803
_cod_original_cell_volume        3814.32(9)
_cod_database_code               4515474
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C44 H32 N2 O2'
_chemical_oxdiff_usercomment     'Hon Eong Ho heh477 (2)'
_shelx_estimated_absorpt_t_max   0.841
_shelx_estimated_absorpt_t_min   0.448
_reflns_odcompleteness_completeness 99.97
_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. Restrained distances
 Cl6-C26 = Cl5-C26
 1.77 with sigma of 0.005
 Cl4-C25 = C25-Cl3
 1.77 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
Uanis(Cl6) = Uanis(C26) = Uanis(Cl5)
Uanis(C23) = Uanis(C26)
Uanis(C24) = Uanis(C25)
4. Others
 Sof(C24)=Sof(H24A)=Sof(H24B)=0.5*FVAR(2)
 Sof(Cl2)=FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=0.5*FVAR(3)
 Sof(Cl1)=FVAR(2)
 Sof(Cl3)=Sof(Cl4)=Sof(C25)=Sof(H25A)=Sof(H25B)=FVAR(3)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(Cl6)=Sof(Cl5)=FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C21(H21), C22(H22)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              28778
_shelx_hkl_checksum              84020
_olex2_date_sample_data_collection 2018-05-15
_olex2_date_sample_submission    2018-05-14
_olex2_exptl_crystal_mounting_method 'oil on micromout'
_olex2_submission_original_sample_id heh477
_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 1.439
_oxdiff_exptl_absorpt_empirical_full_min 0.745