Rhodium-Catalyzed Asymmetric Hydroamination of Allyl Amines.
Vanable, Evan P.; Kennemur, Jennifer L.; Joyce, Leo A.; Ruck, Rebecca T.; Schultz, Danielle M.; Hull, Kami L.; Journal of the American Chemical Society 141 (2019) 739–742; doi:10.1021/jacs.8b09811

data_4128151
_publ_contact_author
; 
 Kami L. Hull 
University of Texas at Austin
2506 Speedway STOP A5300
Austin, Tx, 78712
USA 
;
_publ_section_title
;
 Rhodium-Catalyzed Asymmetric Hydroamination of Allyl Amines.
;
_journal_issue                   2
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              739
_journal_page_last               742
_journal_paper_doi               10.1021/jacs.8b09811
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C7 H7 O3 S), C15 H26 N2 O2'
_chemical_formula_sum            'C29 H40 N2 O8 S2'
_chemical_formula_weight         608.75
_chemical_name_systematic
'4-(1-((4-methoxybenzyl)-l4-azanyl)propan-2-yl)-4l4-morpholine, 4-methylbenzenesulfonate salt'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
?
;
_cell_angle_alpha                97.2030(10)
_cell_angle_beta                 97.0590(10)
_cell_angle_gamma                99.7270(10)
_cell_formula_units_Z            2
_cell_length_a                   6.1734(2)
_cell_length_b                   12.3999(4)
_cell_length_c                   20.4254(6)
_cell_measurement_reflns_used    40516
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      28.35
_cell_measurement_theta_min      2.44
_cell_volume                     1512.23(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            78884
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.372
_diffrn_reflns_theta_min         2.032
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.228
_exptl_absorpt_correction_T_max  0.9952
_exptl_absorpt_correction_T_min  0.9306
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Absorbance corrected via multi-scan method'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_description       needle
_exptl_crystal_F_000             648
_exptl_crystal_preparation
'The compound was prepared by mixing a 2:1 ratio of PTSA*H2O and the starting diamine in 1 mL ethanol, followed by removal of solvent.'
_exptl_crystal_recrystallization_method
'12 mg of the compound was dissolved in 0.6 mL absolute ethanol. This was transferred to a pipette with its bottom melted off. 0.3 mL absolute ethanol was layered on top of this, and then 0.9 mL hexanes was layered above this. The tube was allowed to sit for 3 weeks after which an array of needles had formed within the tube.'
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.124
_exptl_crystal_size_min          0.091
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.548
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 6022 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         15036
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0498
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0442P)^2^+0.9385P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0955
_refine_ls_wR_factor_ref         0.1007
_reflns_Friedel_coverage         0.989
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                13477
_reflns_number_total             15036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09811_si_002.cif
_cod_data_source_block           mo_dd05i_0m
_cod_database_code               4128151
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.923
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C30A) = Uanis(C30B)
Uanis(C15A) = Uanis(C15B)
3. Others
 Sof(C15B)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C15A)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 N3(H3), C17(H17), N1(H1), C2(H2)
4.b Secondary CH2 refined with riding coordinates:
 N4(H4A,H4B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B),
 C22(H22A,H22B), C23(H23A,H23B), N2(H2A,H2B), C3(H3A,H3B), C4(H4C,H4D), C5(H5A,
 H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B)
4.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C33(H33), C35(H35), C36(H36), C25(H25), C26(H26), C28(H28),
 C29(H29), C46(H46), C47(H47), C49(H49), C50(H50), C53(H53), C54(H54), C56(H56),
  C57(H57), C39(H39), C40(H40), C42(H42), C43(H43), C10(H10), C11(H11),
 C13(H13), C14(H14)
4.d Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C16(H16A,H16B,H16C), C51(H51A,H51B,H51C), C58(H58A,H58B,
 H58C), C44(H44A,H44B,H44C), C1(H1A,H1B,H1C), C30A(H30A,H30B,H30C), C15A(H15A,
 H15B,H15C), C30B(H30D,H30E,H30F), C15B(H15D,H15E,H15F)
;
_shelx_res_checksum              38855
_shelx_hkl_checksum              5506
_olex2_date_sample_data_collection 2017-07-18
_olex2_date_sample_submission    2017-07-18
_olex2_exptl_crystal_mounting_method
'Mounted in paratone oil upon a loop after cutting with a razor blade.'
_olex2_submission_original_sample_id MO_DD05I_0M
_olex2_submission_special_instructions 'No special instructions were received'