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_4124153
_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 rmad
_chemical_formula_moiety         'C35 H41 N O7'
_chemical_formula_sum            'C35 H41 N O7'
_chemical_formula_weight         587.69
_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             2015-04-25
_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                   9.3732(6)
_cell_length_b                   10.9685(8)
_cell_length_c                   30.310(2)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.141
_cell_measurement_theta_min      2.916
_cell_volume                     3116.2(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      100.15
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.1051
_diffrn_reflns_av_unetI/netI     0.0642
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            32639
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        63.664
_diffrn_reflns_theta_max         63.664
_diffrn_reflns_theta_min         2.916
_exptl_absorpt_coefficient_mu    0.703
_exptl_absorpt_correction_T_max  0.7420
_exptl_absorpt_correction_T_min  0.5846
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1228 before and 0.1017 after correction.
The Ratio of minimum to maximum transmission is 0.7879.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       plate
_exptl_crystal_F_000             1256
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.580
_refine_diff_density_min         -0.301
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 1450 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.17(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.145
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     393
_refine_ls_number_reflns         5095
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0892
_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^)+(0.0360P)^2^+5.3620P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1490
_refine_ls_wR_factor_ref         0.1578
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                4304
_reflns_number_total             5095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b05528_si_001.cif
_cod_data_source_block           crystal_05
_cod_depositor_comments
'Adding full bibliography for 4124149--4124153.cif.'
_cod_database_code               4124153
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.849
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C22(H22A,H22B), C7(H7A,H7B), C29(H29A,H29B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C28(H28), C27(H27), C25(H25), C12(H12), C24(H24), C16(H16), C15(H15),
 C35(H35), C31(H31), C32(H32), C13(H13), C14(H14), C33(H33), C34(H34)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C9(H9A,H9B,H9C), C21(H21A,H21B,H21C)
2.e Idealised tetrahedral OH refined as rotating group:
 O6(H6)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'