Anti-Markovnikov Hydroamination of Homoallylic Amines.
Ensign, Seth C.; Vanable, Evan P.; Kortman, Gregory D.; Weir, Lee J.; Hull, Kami L.; Journal of the American Chemical Society 137 (2015) 13748–13751; doi:10.1021/jacs.5b08500

data_4129578
_publ_contact_author
; 
Kami L. Hull 
University of Illinois 
361 RAL, Box 23-5 
600 South Mathews Avenue 
Urbana, Illinois  61801 
USA 
;
_publ_section_title
;
 Anti-Markovnikov Hydroamination of Homoallylic Amines.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13748
_journal_page_last               13751
_journal_paper_doi               10.1021/jacs.5b08500
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety
;
C52 H45 N O P2 Rh, C4 H8 O, B F2, 2(F)
;
_chemical_formula_sum            'C56 H53 B F4 N O2 P2 Rh'
_chemical_formula_weight         1023.65
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-02
_audit_creation_method
; 
Olex2 1.2 
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103) 
;
_audit_update_record
; 
? 
;
_cell_angle_alpha                88.2639(19)
_cell_angle_beta                 84.3786(18)
_cell_angle_gamma                73.4287(19)
_cell_formula_units_Z            2
_cell_length_a                   10.5541(6)
_cell_length_b                   10.8702(6)
_cell_length_c                   21.4812(10)
_cell_measurement_reflns_used    9794
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.15
_cell_measurement_theta_min      2.38
_cell_volume                     2350.7(2)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2014.9-0 (Bruker, 2014)'
_computing_data_reduction
; 
SAINT V8.34A, XPREP v2014/2, SADABS V2014/4, TWINABS V2012/1 
(Bruker, 2012 & 2014) 
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
; 
SHELX-2014-6 (Sheldrick, 2014) 
Olex2 1.2.6 (Dolomanov et. al., 2009) 
;
_computing_structure_solution    'SHELX-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 CCD
_diffrn_detector_type            'Apex II CCD'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Bruker D8 Venture/Photon 100'
_diffrn_measurement_method       'profile data from \f and \w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_source         'microfocus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_wavelength_id  mo_cd26w_0m
_diffrn_reflns_av_R_equivalents  0.0694
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            10430
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.159
_diffrn_reflns_theta_min         2.177
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.492
_exptl_absorpt_correction_T_max  0.96925
_exptl_absorpt_correction_T_min  0.95434
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker, 2014)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_id                mo_cd26w_0m
_exptl_crystal_preparation
; 
The data crystal was mounted using oil (Parantone-N, Exxon) to a 
0.3 mm cryo-loop (Hampton Research) with the (1 0 -5) scattering 
planes roughly normal to the spindle axis. 
;
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.117
_refine_diff_density_max         0.374
_refine_diff_density_min         -0.884
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     622
_refine_ls_number_reflns         10430
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0261
_refine_ls_R_factor_gt           0.0233
_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^)+(0.0279P)^2^+1.5053P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0599
_refine_ls_wR_factor_ref         0.0610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10430
_reflns_number_total             10430
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b08500_si_001.cif
_cod_data_source_block           mo_cd26w_0m
_cod_database_code               4129578
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.934
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups, All C(H,H) groups, All N(H,H) groups 
2. Uiso/Uaniso restraints and constraints 
Uanis(B1) = Uanis(B1A) 
Uanis(F3) = Uanis(F3A) 
Uanis(F4) = Uanis(F4A) 
Uanis(F1) = Uanis(F1A) 
Uanis(F2) = Uanis(F2A) 
3. Others 
 Sof(B1A)=Sof(F3A)=Sof(F4A)=1-FVAR(1) 
 Sof(F3)=Sof(F4)=Sof(B1)=FVAR(1) 
 Sof(F1A)=1-FVAR(2) 
 Sof(F1)=FVAR(2) 
 Sof(F2A)=1-FVAR(3) 
 Sof(F2)=FVAR(3) 
4.a Ternary CH refined with riding coordinates: 
 C3(H3) 
4.b Secondary CH2 refined with riding coordinates: 
 N1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C1S(H1SA,H1SB), C2S(H2SA,H2SB), 
 C3S(H3SA,H3SB), C4S(H4SA,H4SB) 
4.c Aromatic/amide H refined with riding coordinates: 
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14), 
 C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), 
  C25(H25), C26(H26), C27(H27), C28(H28), C31(H31), C32(H32), C33(H33), 
 C34(H34), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), 
  C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53) 
;
_shelx_res_checksum              33880
_shelx_hkl_checksum              50577
_olex2_submission_special_instructions 'No special instructions were received'