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_4123522
_publ_section_title
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 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
'0.2(C1 H2 Cl2), C28 H31 N3 O8 S, 0.3(C5 H12)'
_chemical_formula_sum            'C29.7 H34.99 Cl0.4 N3 O8 S'
_chemical_formula_weight         608.26
_chemical_name_systematic
;
 ?
;
_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     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                 105.721(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5147(12)
_cell_length_b                   12.7713(10)
_cell_length_c                   15.9668(12)
_cell_measurement_reflns_used    9976
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      33.17
_cell_measurement_theta_min      2.28
_cell_volume                     3045.4(4)
_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 1.000
_diffrn_measured_fraction_theta_max 0.998
_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  0.0437
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            153616
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         33.387
_diffrn_reflns_theta_min         1.363
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.195
_exptl_absorpt_correction_T_max  0.7466
_exptl_absorpt_correction_T_min  0.6742
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0590 before and 0.0525 after correction.
The Ratio of minimum to maximum transmission is 0.9030.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             1284
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.323
_refine_diff_density_min         -2.558
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Flack x determined using 9141 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.080(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     802
_refine_ls_number_reflns         23614
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.1065
_refine_ls_R_factor_gt           0.0950
_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^)+(0.1100P)^2^+7.9660P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2482
_refine_ls_wR_factor_ref         0.2582
_reflns_Friedel_coverage         0.925
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                21032
_reflns_number_total             23614
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b01944_si_002.cif
_cod_data_source_block           crystal02
_cod_original_formula_sum        'C29.70 H34.99 Cl0.40 N3 O8 S'
_cod_database_code               4123522
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.909
_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. Rigid bond restraints
 C62, C61, C60, C59, C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
4. Others
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=
 Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 Sof(H62C)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(C57)=Sof(H57A)=Sof(H57B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C32(H32), C4(H4)
5.b Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C29(H29A,H29B), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,
 H40B), C41(H41A,H41B), C42(H42A,H42B), C1(H1A,H1B), C10(H10A,H10B), C11(H11A,
 H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C59(H59A,H59B),
 C60(H60A,H60B), C61(H61A,H61B)
5.c Aromatic/amide H refined with riding coordinates:
 C31(H31), C45(H45), C46(H46), C47(H47), C48(H48), C52(H52), C53(H53),
 C55(H55), C56(H56), C3(H3), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24),
 C25(H25), C27(H27), C28(H28)
5.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C7(H7A,H7B,
 H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C58(H58A,H58B,H58C), C62(H62A,H62B,
 H62C)
;