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_4123524
_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         'C18 H24 N2 O7 S'
_chemical_formula_sum            'C18 H24 N2 O7 S'
_chemical_formula_weight         412.45
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2014-12-10
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.879(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.0897(16)
_cell_length_b                   10.667(2)
_cell_length_c                   11.916(2)
_cell_measurement_reflns_used    9576
_cell_measurement_temperature    293
_cell_measurement_theta_max      29.01
_cell_measurement_theta_min      2.52
_cell_volume                     1025.9(3)
_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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      293
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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  0.0572
_diffrn_reflns_av_unetI/netI     0.0376
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            51336
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.575
_diffrn_reflns_theta_min         1.713
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.199
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9427
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0560 before and 0.0470 after correction.
The Ratio of minimum to maximum transmission is 0.9427.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_description       block
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.65
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2336 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.923
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         9346
_refine_ls_number_restraints     41
_refine_ls_restrained_S_all      0.924
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0750P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1057
_refine_ls_wR_factor_ref         0.1168
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                6016
_reflns_number_total             9346
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01944_si_002.cif
_cod_data_source_block           crystal04
_cod_database_code               4123524
_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
 C12-C10 \\sim C11-C10 \\sim C13-C10 \\sim C12A-C10 \\sim C11A-C10 \\sim
C13A-C10
 with sigma of 0.02
 O3-C9 \\sim C9-O3A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C12 \\sim C12A: within 1.7A with sigma of 0.03 and sigma for terminal atoms of
0.06
C13 \\sim C13A: within 1.7A with sigma of 0.03 and sigma for terminal atoms of
0.06
C11 \\sim C11A: within 1.7A with sigma of 0.03 and sigma for terminal atoms of
0.06
O3 \\sim O3A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
4. Others
 Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12A)=Sof(H12D)=Sof(H12E)=
 Sof(H12F)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(1)
 Sof(O3A)=1-FVAR(2)
 Sof(O3)=FVAR(2)
 Fixed X: C11(1.204469)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C5(H5)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B), C7(H7A,H7B)
5.c Me refined with riding coordinates:
 C11(H11A,H11B,H11C), C11A(H11D,H11E,H11F), C12(H12A,H12B,H12C), C12A(H12D,
 H12E,H12F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F)
5.d Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C18(H18), C19(H19)
5.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C)
;
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method fiber
_olex2_submission_special_instructions 'No special instructions were received'