Use of a New Spirophosphine To Achieve Catalytic Enantioselective [4 + 1] Annulations of Amines with Allenes To Generate Dihydropyrroles
Kramer, Søren; Fu, Gregory C.; Journal of the American Chemical Society  (2015) 150317085953008–; doi:10.1021/jacs.5b01944

data_4123523
_publ_section_title
;
 Use of a New Spirophosphine To Achieve Catalytic Enantioselective [4 + 1]
 Annulations of Amines with Allenes To Generate Dihydropyrroles
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              150317085953008
_journal_paper_doi               10.1021/jacs.5b01944
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H24 N2 O6 S'
_chemical_formula_sum            'C22 H24 N2 O6 S'
_chemical_formula_weight         444.49
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-07
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                104.122(3)
_cell_angle_beta                 93.894(3)
_cell_angle_gamma                90.639(3)
_cell_formula_units_Z            1
_cell_length_a                   7.7594(4)
_cell_length_b                   8.0085(4)
_cell_length_c                   8.9723(4)
_cell_measurement_reflns_used    9141
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.56
_cell_measurement_theta_min      2.35
_cell_volume                     539.23(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0673
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            31423
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         37.823
_diffrn_reflns_theta_min         2.347
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.192
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.369
_exptl_crystal_description       Block
_exptl_crystal_F_000             234
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.475
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 3740 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.006(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.926
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     282
_refine_ls_number_reflns         10936
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.926
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0310P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0702
_refine_ls_wR_factor_ref         0.0732
_reflns_Friedel_coverage         0.960
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.923
_reflns_number_gt                8915
_reflns_number_total             10936
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01944_si_002.cif
_cod_data_source_block           crystal03
_cod_database_code               4123523
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.963
_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)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C5(H5A,H5B), C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C11(H11), C12(H12), C14(H14), C15(H15), C18(H18), C19(H19), C20(H20),
 C21(H21), C22(H22)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;