Enantioselective synthesis of bicyclo[3.n.1]alkanes by chiral phosphoric acid-catalyzed desymmetrizing Michael cyclizations
Burns, Alan R.; Madec, Amaël G. E.; Low, Darryl W.; Roy, Iain D.; Lam, Hon Wai; Chem. Sci. 6 (2015) 3550–; doi:10.1039/C5SC00753D

data_1519409
_publ_section_title
;
 Enantioselective synthesis of bicyclo[3.n.1]alkanes by chiral phosphoric
 acid-catalyzed desymmetrizing Michael cyclizations
;
_journal_issue                   6
_journal_name_full               'Chem. Sci.'
_journal_page_first              3550
_journal_paper_doi               10.1039/C5SC00753D
_journal_volume                  6
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H17 Cl O3'
_chemical_formula_sum            'C17 H17 Cl O3'
_chemical_formula_weight         304.76
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_audit_update_record
;
2015-01-22 deposited with the CCDC.
2015-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.2836(3)
_cell_length_b                   12.6214(7)
_cell_length_c                   37.0026(17)
_cell_measurement_reflns_used    10588
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.3450
_cell_measurement_theta_min      3.5050
_cell_volume                     2934.6(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2013)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3271
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.2437810000
_diffrn_orient_matrix_UB_12      0.0087422000
_diffrn_orient_matrix_UB_13      -0.0033096000
_diffrn_orient_matrix_UB_21      0.0211456000
_diffrn_orient_matrix_UB_22      0.1192819000
_diffrn_orient_matrix_UB_23      -0.0080357000
_diffrn_orient_matrix_UB_31      0.0157101000
_diffrn_orient_matrix_UB_32      -0.0242747000
_diffrn_orient_matrix_UB_33      -0.0407196000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            21694
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.490
_diffrn_reflns_theta_min         3.700
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    2.369
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.909
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       block
_exptl_crystal_F_000             1280
_exptl_crystal_size_max          0.4467
_exptl_crystal_size_mid          0.3345
_exptl_crystal_size_min          0.2333
_refine_diff_density_max         0.225
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2396 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     381
_refine_ls_number_reflns         5961
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0279
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0414P)^2^+0.3964P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0709
_refine_ls_wR_factor_ref         0.0716
_reflns_Friedel_coverage         0.730
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                5804
_reflns_number_total             5961
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5sc00753d2.cif
_cod_data_source_block           amhwlb
_cod_depositor_comments
'Adding full bibliography for 1519409--1519412.cif.'
_cod_database_code               1519409
_nottingham_internal_coll_name   AMHWLB
_nottingham_internal_coll_number 13644
_nottingham_internal_coll_client AM/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '3.0000, 2.0000'
_nottingham_internal_coll_frame_width 2.0000
_nottingham_internal_coll_user   pczwl
_nottingham_internal_coll_date   28/05/2014
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_date 28/05/2014
_nottingham_internal_process_user pczwl
_nottingham_internal_solution_date 28/5/2014
_nottingham_internal_solution_user pczwl
_nottingham_internal_refinement_date 28/5/2014
_nottingham_internal_refinement_user pczwl
_nottingham_internal_validation_date 28/5/2014
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 28/5/2014
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         'C17 H17 O3 Cl'
_reflns_odcompleteness_completeness 99.64
_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.a Ternary CH refined with riding coordinates:
 C4(H4), C6(H6), C35(H35), C37(H37)
2.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C7(H7A,H7B), C8(H8A,H8B), C12(H12A,H12B), C33(H33A,H33B),
 C38(H38A,H38B), C39(H39A,H39B), C43(H43A,H43B)
2.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C17(H17), C19(H19), C20(H20), C47(H47), C48(H48), C50(H50), C51(H51)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C40(H40A,H40B,H40C)
;
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'