Development and Investigation of an Organocatalytic Enantioselective [10 + 2] Cycloaddition
McLeod, David; Izzo, Joseph A.; Jørgensen, Danny K. B.; Lauridsen, Rune F.; Jørgensen, Karl Anker; ACS Catalysis  (2020) 10784–; doi:10.1021/acscatal.0c03378

data_4518020
_publ_section_title
;
 Development and Investigation of an Organocatalytic Enantioselective [10
 + 2] Cycloaddition
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10784
_journal_paper_doi               10.1021/acscatal.0c03378
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H25 Br O2'
_chemical_formula_sum            'C27 H25 Br O2'
_chemical_formula_weight         461.38
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                97.438(3)
_cell_angle_beta                 97.121(2)
_cell_angle_gamma                90.238(2)
_cell_formula_units_Z            4
_cell_length_a                   9.6954(2)
_cell_length_b                   10.1078(4)
_cell_length_c                   22.4793(8)
_cell_measurement_reflns_used    12507
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      27.7890
_cell_measurement_theta_min      2.1960
_cell_volume                     2167.11(13)
_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      100.0(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.960
_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     74.00 123.00   1.00   17.89    --   22.77 132.00 -11.00   49
  2  \w     70.00 124.00   1.00   17.89    --   22.77 137.00 165.00   54
  3  \w     10.00  96.00   1.00   17.89    --   22.77-132.00 -80.00   86
  4  \w    -97.00 -10.00   1.00   17.89    --  -23.55 132.00 -11.00   87
  5  \w   -124.00 -74.00   1.00   17.89    --  -23.55-132.00 -80.00   50
  6  \w   -100.00 -13.00   1.00   17.89    --  -23.55 137.00 165.00   87
  7  \w   -125.00 -70.00   1.00   17.89    --  -23.55-137.00 102.00   55
  8  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00-120.00   68
  9  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00 150.00   68
 10  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00 -90.00   68
 11  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00 -60.00   68
 12  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00   0.00   68
 13  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00  60.00   68
 14  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00 -30.00   68
 15  \w    -26.00  42.00   1.00   17.89    --   22.77  77.00-150.00   68
 16  \w    -15.00  32.00   1.00   17.89    --  -23.55 -99.00  90.00   47
 17  \w    -15.00  32.00   1.00   17.89    --  -23.55 -99.00 120.00   47
 18  \w    -15.00  32.00   1.00   17.89    --  -23.55 -99.00  30.00   47
 19  \w   -132.00 -82.00   1.00   17.89    --  -23.55 -77.00 150.00   50
 20  \w     82.00 128.00   1.00   17.89    --   22.77  77.00 -30.00   46
 21  \w    -78.00 -28.00   1.00   17.89    --   22.77 -38.00  30.00   50
 22  \w     82.00 128.00   1.00   17.89    --   22.77  77.00-180.00   46
 23  \w    -36.00 124.00   1.00   17.89    --   22.77  38.00  60.00  160
 24  \w   -132.00 -82.00   1.00   17.89    --  -23.55 -77.00-180.00   50
 25  \w   -132.00 -82.00   1.00   17.89    --  -23.55 -77.00 -30.00   50
 26  \w   -132.00 -82.00   1.00   17.89    --  -23.55 -77.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0041613000
_diffrn_orient_matrix_UB_12      -0.0440709000
_diffrn_orient_matrix_UB_13      0.0222520000
_diffrn_orient_matrix_UB_21      -0.0105140000
_diffrn_orient_matrix_UB_22      -0.0552470000
_diffrn_orient_matrix_UB_23      -0.0230950000
_diffrn_orient_matrix_UB_31      0.0728709000
_diffrn_orient_matrix_UB_32      -0.0039839000
_diffrn_orient_matrix_UB_33      -0.0005273000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0600
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            20990
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.919
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.274
_diffrn_reflns_theta_min         1.842
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.918
_exptl_absorpt_correction_T_max  0.803
_exptl_absorpt_correction_T_min  0.644
_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            'clear yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.289
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.123
_refine_diff_density_max         0.805
_refine_diff_density_min         -0.728
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Flack x determined using 7011 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.028(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     981
_refine_ls_number_reflns         20990
_refine_ls_number_restraints     1321
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0519
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0668P)^2^+0.6099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1109
_refine_ls_wR_factor_ref         0.1128
_reflns_Friedel_coverage         0.915
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.878
_reflns_number_gt                18868
_reflns_number_total             20990
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9777\% 
 around [0.96 -0.00 -0.28] (reciprocal) or [1.00 0.00 0.00] (direct)
;
_cod_data_source_file            cs0c03378_si_002.cif
_cod_data_source_block           dave_kaj_twin1_hklf4
_cod_original_cell_volume        2167.11(12)
_cod_database_code               4518020
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C27 H25 Br O2'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5582(10)
 0.4418(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
3. Rigid bond restraints
 C6C, C5C, C5, C4C, C17, C14C, C4, C24B, C19, C24C, C18C, C23, C16, C6, C15,
 C19C, C20C, C23B, C20, C3C, C3, C23C, C6B, C17A, C7A, C8B, C2C, C24, C22, C4B,
 C15C, C5B, C3B, C10C, C3A, C27B, C16A, C22C, C5A, C27, C27C, C20A, C21, C17C,
 C1B, C22A, C18, C13A, C14, C2B, C1, C16C, C18A, C15A, C2A, C22B, C21C, C26B,
 C4A, C24A, C2, C1A, C10B, C14A, C9, C12A, C1C, C8A, C13C, C25C, C15B, C10, C7,
 C13, C21B, C10A, C14B, C25B, C9B, C20B, C6A, C25, C7B, C11B, C16B, C7C, C26,
 C21A, C11A, C8, C18B, C11C, C9A, C9C, C13B, C12, C17B, C25A, C11, C26C, C19B,
 C19A, C23A, C26A, C8C, C12C, C27A, C12B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O2B) \\sim Ueq, Uanis(O2C) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C17C) = Uanis(C18) = Uanis(C23B) = Uanis(C18A)
Uanis(C1B) = Uanis(C1C) = Uanis(C1) = Uanis(C1A)
Uanis(C3A) = Uanis(C5) = Uanis(C3B) = Uanis(C3C)
Uanis(C4B) = Uanis(C4C) = Uanis(C4) = Uanis(C4A)
Uanis(O1) = Uanis(O1A) = Uanis(O1B) = Uanis(O1C)
Uanis(O2B) = Uanis(O2C) = Uanis(O1A) = Uanis(O2)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 C7A(H7A), C8B(H8B), C10C(H10C), C27B(H27B), C14(H14), C10B(H10B), C14A(H14A),
 C8A(H8A), C13C(H13C), C10(H10), C7(H7), C10A(H10A), C7B(H7B), C7C(H7C), C8(H8),
  C8C(H8C)
6.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C12A(H12E,H12F), C9B(H9BA,H9BB), C11B(H11C,H11D), C11A(H11E,
 H11F), C11C(H11A,H11B), C9A(H9AA,H9AB), C9C(H9CA,H9CB), C12(H12G,H12H),
 C11(H11G,H11H), C12C(H12A,H12B), C12B(H12C,H12D)
6.c Aromatic/amide H refined with riding coordinates:
 C6C(H6C), C5C(H5C), C5(H5), C17(H17), C24B(H24B), C19(H19), C24C(H24C),
 C18C(H18C), C23(H23), C16(H16), C6(H6), C23B(H23B), C3C(H3C), C3(H3),
 C23C(H23C), C6B(H6B), C17A(H17A), C2C(H2CA), C24(H24), C15C(H15C), C5B(H5B),
 C3B(H3B), C3A(H3A), C16A(H16A), C5A(H5A), C27(H27), C27C(H27C), C17C(H17C),
 C18(H18), C2B(H2BA), C16C(H16C), C18A(H18A), C2A(H2AA), C22B(H22B), C24A(H24A),
  C2(H2D), C25C(H25C), C25B(H25B), C20B(H20B), C6A(H6A), C25(H25), C16B(H16B),
 C26(H26), C18B(H18B), C17B(H17B), C25A(H25A), C26C(H26C), C19B(H19B),
 C19A(H19A), C23A(H23A), C26A(H26A), C27A(H27A)
6.d Tetrahedral OH refined with riding coordinates:
 O2B(H2B)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1C(H1C), O1B(H1B), O1A(H1A), O2A(H2A), O2C(H2C), O2(H2)
;
_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 1.244
_oxdiff_exptl_absorpt_empirical_full_min 0.743
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2