Asymmetric Synthesis of β-Amino Amides by Catalytic Enantioconvergent 2-Aza-Cope Rearrangement.
Goodman, C. Guy; Johnson, Jeffrey S.; Journal of the American Chemical Society 137 (2015) 14574–14577; doi:10.1021/jacs.5b09593

data_4129693
_publ_section_title
;
 Asymmetric Synthesis of \b-Amino Amides by Catalytic Enantioconvergent
 2-Aza-Cope Rearrangement.
;
_journal_issue                   46
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14574
_journal_page_last               14577
_journal_paper_doi               10.1021/jacs.5b09593
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H32 N2 O2'
_chemical_formula_sum            'C26 H32 N2 O2'
_chemical_formula_weight         404.53
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-04
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.166(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.4808(6)
_cell_length_b                   24.6772(17)
_cell_length_c                   10.9388(7)
_cell_measurement_reflns_used    9928
_cell_measurement_temperature    100
_cell_measurement_theta_max      70.06
_cell_measurement_theta_min      3.58
_cell_volume                     2271.4(3)
_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    'olex2.solve (Bourhis et al., 2015)'
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            78684
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.135
_diffrn_reflns_theta_min         3.582
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.583
_exptl_absorpt_correction_T_max  0.9430
_exptl_absorpt_correction_T_min  0.8620
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0701 before and 0.0595 after correction.
The Ratio of minimum to maximum transmission is 0.9141.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_description       block
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.248
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.188
_refine_diff_density_max         0.423
_refine_diff_density_min         -0.416
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 3142 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     545
_refine_ls_number_reflns         8567
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0875P)^2^+0.6624P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1429
_refine_ls_wR_factor_ref         0.1480
_reflns_Friedel_coverage         0.940
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                7640
_reflns_number_total             8567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b09593_si_001.cif
_cod_data_source_block           x1506001
_cod_database_code               4129693
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.869
_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:
 C9(H9), C10(H10), C28(H28), C39(H39), C40(H40), C58(H58)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C25(H25A,H25B), C32(H32A,
 H32B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C55(H55A,H55B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
 C22(H22), C23(H23), C24(H24), C26(H26), C44(H44), C45(H45), C46(H46), C47(H47),
  C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56)
2.d X=CH2 refined with riding coordinates:
 C27(H27A,H27B), C57(H57A,H57B)
2.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C)
;
_shelx_res_checksum              70144
_shelx_hkl_checksum              99423
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id 3294-1
_olex2_submission_special_instructions 'No special instructions were received'