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_4123521
_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 rmad
_chemical_formula_moiety         'C27 H28 P, 0.5(C4 H8 O), B F4'
_chemical_formula_sum            'C29 H32 B F4 O0.5 P'
_chemical_formula_weight         506.32
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.213(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4149(17)
_cell_length_b                   16.705(3)
_cell_length_c                   16.720(3)
_cell_measurement_reflns_used    9945
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.02
_cell_measurement_theta_min      2.44
_cell_volume                     2549.2(8)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_device_type  'Bruker DUO'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1032
_diffrn_reflns_av_unetI/netI     0.1397
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            147003
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         37.152
_diffrn_reflns_theta_min         2.438
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.156
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9475
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
'SADABS-2014/2 (Bruker,2014) was used for absorption correction. wR2(int) 
was 0.0981 before and 0.0717 after correction. The Ratio of minimum to 
maximum transmission is 0.9475. The \l/2 correction factor is 0.00150.'
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.547
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.087
_refine_ls_abs_structure_details
;
 Flack x determined using 5561 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     662
_refine_ls_number_reflns         24551
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.1525
_refine_ls_R_factor_gt           0.0716
_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^)+(0.0450P)^2^+0.8920P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1119
_refine_ls_wR_factor_ref         0.1303
_reflns_Friedel_coverage         0.901
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.912
_reflns_number_gt                15272
_reflns_number_total             24551
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01944_si_002.cif
_cod_data_source_block           crystal01
_cod_original_cell_volume        2549.3(8)
_cod_original_formula_sum        'C29 H32 B F4 O0.50 P'
_cod_database_code               4123521
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O1 \\sim O1A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
3. Others
 Sof(H55C)=Sof(H55D)=Sof(H58C)=Sof(H58D)=Sof(O1A)=1-FVAR(1)
 Sof(H55A)=Sof(H55B)=Sof(H58A)=Sof(H58B)=Sof(O1)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C28(H28), C46(H46), C1(H1A), C19(H19)
4.b Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C55(H55A,H55B), C55(H55C,H55D),
  C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C58(H58C,H58D)
4.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C31(H31), C32(H32), C43(H43), C44(H44), C45(H45), C50(H50),
 C51(H51), C52(H52), C53(H53), C54(H54), C3(H3), C4(H4), C5(H5), C15(H15),
 C16(H16), C17(H17), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27)
4.d Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'