Phosphine-Catalyzed Doubly Stereoconvergent γ-Additions of Racemic Heterocycles to Racemic Allenoates: The Catalytic Enantioselective Synthesis of Protected α,α-Disubstituted α-Amino Acid Derivatives.
Kalek, Marcin; Fu, Gregory C.; Journal of the American Chemical Society 137 (2015) 9438–9442; doi:10.1021/jacs.5b05528

data_4124150
_publ_section_title
;
 Phosphine-Catalyzed Doubly Stereoconvergent \g-Additions of Racemic
 Heterocycles to Racemic Allenoates: The Catalytic Enantioselective
 Synthesis of Protected \a,\a-Disubstituted \a-Amino Acid Derivatives.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9438
_journal_page_last               9442
_journal_paper_doi               10.1021/jacs.5b05528
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H39 N O5'
_chemical_formula_sum            'C35 H39 N O5'
_chemical_formula_weight         553.67
_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     direct
_audit_creation_date             2015-05-20
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6834(4)
_cell_length_b                   16.2787(7)
_cell_length_c                   21.3864(9)
_cell_measurement_reflns_used    9813
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.08
_cell_measurement_theta_min      3.41
_cell_volume                     3023.1(2)
_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      100.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Photon CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            73998
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.193
_diffrn_reflns_theta_min         3.412
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.644
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.5075
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1532 before and 0.0762 after correction.
The Ratio of minimum to maximum transmission is 0.6737.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_description       block
_exptl_crystal_F_000             1184
_exptl_crystal_size_max          0.84
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.346
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 2472 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     374
_refine_ls_number_reflns         5754
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0615P)^2^+0.4149P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0923
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5724
_reflns_number_total             5754
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b05528_si_001.cif
_cod_data_source_block           crystal_02
_cod_depositor_comments
'Adding full bibliography for 4124149--4124153.cif.'
_cod_database_code               4124150
_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:
 C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C10(H10A,H10B), C22(H22A,H22B), C29(H29A,H29B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C24(H24),
 C25(H25), C27(H27), C28(H28), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'