Rhodium(II)-catalyzed alkyne amination of homopropargylic sulfamate esters: stereoselective synthesis of functionalized norcaradienes by arene cyclopropanation.
Brawn, Ryan A.; Zhu, Kaicheng; Panek, James S.; Organic letters 16 (2014) 74–77; doi:10.1021/ol403035g

data_1513533
_publ_section_title
;
 Rhodium(II)-catalyzed alkyne amination of homopropargylic sulfamate
 esters: stereoselective synthesis of functionalized norcaradienes by
 arene cyclopropanation.
;
_journal_issue                   1
_journal_name_full               'Organic letters'
_journal_page_first              74
_journal_page_last               77
_journal_paper_doi               10.1021/ol403035g
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         '4(C16 H21 N O6 S), C4 H8 O'
_chemical_formula_sum            'C68 H92 N4 O25 S4'
_chemical_formula_weight         1493.74
_space_group_IT_number           20
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'C 2c 2'
_symmetry_space_group_name_H-M   'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_audit_update_record
;
2011-07-11 # Formatted by publCIF
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.9248(19)
_cell_length_b                   15.416(2)
_cell_length_c                   39.310(6)
_cell_measurement_reflns_used    9318
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.080
_cell_measurement_theta_min      4.463
_cell_volume                     7832.5(19)
_computing_cell_refinement       'SAINT (Bruker, 2006)'
_computing_data_collection       'APEX2 (Bruker, 2006)'
_computing_data_reduction        'SAINT (Bruker, 2006)'
_computing_molecular_graphics    'OLEX2 (Dolmanov, et al. 2009)'
_computing_publication_material  'PublCIF v.1.9.5_c (IUCr)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker Proteum-R'
_diffrn_measurement_method       '\w & \f scans'
_diffrn_radiation_monochromator  multilayer
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0442
_diffrn_reflns_av_sigmaI/netI    0.0193
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            72674
_diffrn_reflns_theta_full        66.68
_diffrn_reflns_theta_max         66.68
_diffrn_reflns_theta_min         2.25
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.754
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6550
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             3168
_exptl_crystal_size_max          0.158
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.065
_platon_squeeze_details
;

TITL brawn5_0m in C222(1)                                                      
CELL   12.9248   15.4160   39.3100     90.00     90.00     90.00
SPGR C2221       
C101 0.841 0.037-0.001 !       4.82 eA-3
C102 0.031 0.038 0.502 !       3.43 eA-3

Discussion:  The structure includes one tetrahydrofuran
(THF) molecule disordered around a twofold axis, which was refined
anisotropically using a PART -1 instruction in SHELXL with distance and angle
restraints. A second solvent region was highly disordered and atomic
positions could not be resolved. PLATON/SQUEEZE (Spek, 2005) was used to mask
the contribution of this diffuse electron density to the diffraction pattern
after modeling the ordered part of the structure.  The program output 
indicated a single void space in the asymmetric unit near the origin 
possessing only 4-fold multiplicity since it coincides with twofold axes in 
the a and b directions.  The void space is most likely partially occupied
by THF, but the unsuccessful modeling of the electron density peaks precludes 
identificationof any solvent molecule(s) present.  The solvent-accessible 
volume of this region is 163 cubic Angstroms, which is in between the typical 
volumes for one and two THF solvent molecules.  The electron count in the 
void is 44, fewer than the number of electrons in a single THF molecule, 
suggesting partial solvent loss.
;
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.228
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.023(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     486
_refine_ls_number_reflns         6748
_refine_ls_number_restraints     70
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0374
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0273P)^2^+12.5981P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0879
_refine_ls_wR_factor_ref         0.0884
_reflns_number_gt                6552
_reflns_number_total             6748
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol403035g_si_004.cif
_cod_data_source_block           brawn5_0m
_cod_original_cell_volume        7833(2)
_cod_original_sg_symbol_H-M      'C2 2 21'
_cod_database_code               1513533