tert-Butyl (2-phenyl-1,2-dihydro-1-naphth­yl)carbamate

Dockendorff, C.; Lautens, M.; Lough, A.J.

doi:10.1107/S1600536805039747

tert-Butyl (2-phenyl-1,2-dihydro-1-naphthyl)carbamate

C. Dockendorff, M. Lautens and A. J. Lough

In the title molecule, C₂₁H₂₃NO₂, the phenyl ring and the fused benzene ring of the naphthyl system form a dihedral angle of 64.22 (5) Å. The cyclohexene ring is in a half-chair conformation. In the crystal structure, molecules are linked into one-dimensional chains in the b-axis direction via intermolecular N—H

O [N

O = 3.3517 (15) Å] hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039747/bt6794sup1.cif Contains datablocks global, 2
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039747/bt67942sup2.hkl Contains datablock 2

CCDC reference: 296524

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.002 Å
R factor = 0.045
wR factor = 0.126
Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.824     0.991
            Tmin(prime) and Tmax expected:      0.964     0.986
            RR(prime) =      0.850
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.85

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The addition of carbon-based nucleophiles to activated alkenes represents one of the fundamental methods for the controlled construction of carbon–carbon bonds in organic synthesis. To this end, we have reported that heterobicyclic alkenes are effective substrates for metal-catalysed ring-opening reactions with a variety of nucleophiles (for a review, see: Lautens, Fagnou & Hiebert, 2003). One example of such a reaction is the Pd(II)-catalysed ring-opening addition of boronic acids to heterobicyclic alkenes (Lautens & Dockendorff, 2003). This reaction is particularly useful for the synthesis of 1-aminotetralin scaffolds via the ring-opening of azabicyclic alkenes such as (1). Here we report the crystal structure of dihydronaphthalene (2) derived from the Pd(II)-catalysed ring-opening of azabicycle (1) with phenylboronic acid.

The title molecule is shown in Fig. 1. A l l bond lengths and angles are within the expected ranges (Allen et al., 1987). The benzene ring of the naphthalen-1-yl moiety (C2–C7) and the phenyl ring (C11–C16) form a dihedral angle of 64.22 (5)°. In the cyclohexene ring the atoms C2, C7, C8 and C9 form a plane with an r.m.s. deviation 0.023 Å, while atoms C1 and C10 are −0.225 (3) and 0.203 (3) Å from this plane respectively. The conformation analysis of that ring (Duax et al., 1976) shows that the conformation is a half-chair, with a local pseudo-twofold axis running through the midpoints of the C7—C8 and C1—C10 bonds. In the crystal structure, molecules related by unit-cell translations are linked via intermolecular N—H···O hydrogen bonds to form extended C4 chains (Bernstein et al., 1995) in the b-axis direction (Table 1 and Fig. 1).

Experimental top

Azabicycle (1) (5 g, 20.55 mmol), phenylboronic acid (3.76 g, 30.84 mmol), and (bis-1,3-diphenylphosphinopropane)palladium(II)dichloride (0.121 g, 0.205 mmol, 0.01 eq.) were added to a 250 ml round-bottom flask with stir bar. The flask was sealed with a septum and evacuated/flushed with nitrogen three times. Methanol (75 ml) was added by syringe, followed by saturated aqueous solution of Cs₂CO₃ (5M, 4.1 ml, 1 eq.). The flask was put in an oil bath at 333 K and the reaction was heated for 1.5 h, after which time NMR analysis indicated that reaction was complete. The reaction was adsorbed onto a minimum amount of silica gel and purified by flash column (4" x 6" silica gel, eluted with 2–10% EtOAc/hexanes). Yield = 98%. X-ray quality crystals were obtained from an analogous reaction on a smaller scale. The crude reaction mixture, still as a solution in methanol, was stored in a sealed flask in a 258 K freezer for an extended period, after which time crystallization occurred.

Computing details top

Data collection: COLLECT (Nonius, 2003); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL/PC (Sheldrick, 2001); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures top

	Fig. 1. View of (2), showing 30% probability displacement ellipsoids. (arbitrary spheres for the H atoms).
	Fig. 2. A partial packing plot (Spek, 2003) of (2), showing hydrogen bonds as dashed lines.

tert-Butyl (2-phenyl-1,2-dihydro-1-naphthyl)carbamate top

Crystal data top

C₂₁H₂₃NO₂	F(000) = 1376
M_r = 321.40	D_x = 1.224 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 12640 reflections
a = 29.4222 (10) Å	θ = 3.2–27.5°
b = 5.4655 (1) Å	µ = 0.08 mm⁻¹
c = 21.7842 (7) Å	T = 150 K
β = 95.4570 (13)°	Needle, colourless
V = 3487.18 (18) Å³	0.46 × 0.22 × 0.18 mm
Z = 8

Data collection top

Bruker–Nonius KappaCCD diffractometer	3901 independent reflections
Radiation source: fine-focus sealed tube	2869 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ scans and ω scans with κ offsets	h = −38→37
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −6→7
T_min = 0.824, T_max = 0.991	l = −25→28
12640 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0567P)² + 1.1855P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3901 reflections	Δρ_max = 0.17 e Å⁻³
218 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXTL/PC, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0085 (13)

Crystal data top

C₂₁H₂₃NO₂	V = 3487.18 (18) Å³
M_r = 321.40	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 29.4222 (10) Å	µ = 0.08 mm⁻¹
b = 5.4655 (1) Å	T = 150 K
c = 21.7842 (7) Å	0.46 × 0.22 × 0.18 mm
β = 95.4570 (13)°

Data collection top

Bruker–Nonius KappaCCD diffractometer	3901 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	2869 reflections with I > 2σ(I)
T_min = 0.824, T_max = 0.991	R_int = 0.042
12640 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.02	Δρ_max = 0.17 e Å⁻³
3901 reflections	Δρ_min = −0.15 e Å⁻³
218 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.85856 (4)	−0.25880 (18)	0.61630 (5)	0.0543 (3)
O2	0.85041 (3)	0.05403 (16)	0.68345 (4)	0.0451 (3)
N1	0.86220 (4)	0.1397 (2)	0.58723 (5)	0.0406 (3)
H1A	0.8580	0.2928	0.5978	0.049*
C1	0.87440 (4)	0.0824 (2)	0.52536 (6)	0.0391 (3)
H1B	0.8784	−0.0991	0.5239	0.047*
C2	0.83505 (4)	0.1441 (2)	0.47747 (6)	0.0395 (3)
C3	0.79637 (5)	−0.0027 (3)	0.47230 (7)	0.0497 (4)
H3A	0.7955	−0.1449	0.4973	0.060*
C4	0.75908 (5)	0.0545 (3)	0.43148 (7)	0.0566 (4)
H4A	0.7329	−0.0484	0.4282	0.068*
C5	0.75992 (5)	0.2612 (3)	0.39560 (7)	0.0541 (4)
H5A	0.7343	0.3015	0.3676	0.065*
C6	0.79787 (5)	0.4095 (3)	0.40024 (6)	0.0498 (4)
H6A	0.7980	0.5532	0.3757	0.060*
C7	0.83619 (5)	0.3519 (2)	0.44045 (6)	0.0407 (3)
C8	0.87733 (5)	0.5035 (3)	0.44443 (7)	0.0507 (4)
H8A	0.8767	0.6542	0.4226	0.061*
C9	0.91561 (5)	0.4371 (3)	0.47759 (7)	0.0500 (4)
H9A	0.9409	0.5463	0.4805	0.060*
C10	0.92049 (5)	0.1962 (3)	0.51068 (6)	0.0463 (3)
H10A	0.9333	0.0807	0.4811	0.056*
C11	0.95539 (5)	0.2051 (3)	0.56659 (6)	0.0466 (3)
C12	0.95671 (5)	0.3987 (3)	0.60785 (7)	0.0576 (4)
H12A	0.9356	0.5294	0.6008	0.069*
C13	0.98823 (6)	0.4046 (4)	0.65906 (8)	0.0683 (5)
H13A	0.9883	0.5378	0.6871	0.082*
C14	1.01947 (6)	0.2192 (4)	0.66969 (8)	0.0699 (5)
H14A	1.0414	0.2243	0.7046	0.084*
C15	1.01869 (6)	0.0261 (4)	0.62926 (8)	0.0676 (5)
H15A	1.0402	−0.1029	0.6362	0.081*
C16	0.98679 (5)	0.0185 (3)	0.57846 (7)	0.0550 (4)
H16A	0.9864	−0.1173	0.5512	0.066*
C17	0.85738 (4)	−0.0414 (2)	0.62807 (6)	0.0390 (3)
C18	0.84493 (5)	−0.1084 (2)	0.73637 (6)	0.0440 (3)
C19	0.84020 (7)	0.0726 (3)	0.78792 (7)	0.0635 (5)
H19A	0.8127	0.1715	0.7782	0.095*
H19B	0.8670	0.1796	0.7923	0.095*
H19C	0.8378	−0.0161	0.8266	0.095*
C20	0.88728 (6)	−0.2651 (3)	0.75037 (8)	0.0627 (4)
H20A	0.8898	−0.3813	0.7166	0.094*
H20B	0.8850	−0.3551	0.7889	0.094*
H20C	0.9144	−0.1601	0.7547	0.094*
C21	0.80191 (6)	−0.2603 (3)	0.72409 (8)	0.0622 (4)
H21A	0.8058	−0.3772	0.6909	0.093*
H21B	0.7760	−0.1525	0.7118	0.093*
H21C	0.7961	−0.3493	0.7616	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0777 (7)	0.0401 (6)	0.0467 (6)	0.0025 (5)	0.0135 (5)	0.0024 (4)
O2	0.0615 (6)	0.0412 (5)	0.0341 (5)	0.0002 (4)	0.0117 (4)	0.0039 (4)
N1	0.0484 (6)	0.0391 (6)	0.0356 (6)	0.0041 (5)	0.0098 (5)	0.0034 (4)
C1	0.0422 (7)	0.0418 (7)	0.0341 (7)	0.0053 (5)	0.0075 (5)	0.0018 (5)
C2	0.0435 (7)	0.0421 (7)	0.0337 (6)	0.0048 (5)	0.0077 (5)	−0.0012 (5)
C3	0.0499 (8)	0.0537 (8)	0.0461 (8)	−0.0021 (6)	0.0071 (6)	0.0059 (6)
C4	0.0458 (8)	0.0698 (10)	0.0540 (9)	−0.0057 (7)	0.0039 (7)	−0.0007 (8)
C5	0.0489 (8)	0.0687 (10)	0.0439 (8)	0.0105 (7)	−0.0005 (6)	−0.0011 (7)
C6	0.0604 (9)	0.0494 (8)	0.0389 (8)	0.0106 (7)	0.0013 (6)	0.0035 (6)
C7	0.0490 (7)	0.0405 (7)	0.0328 (7)	0.0048 (6)	0.0054 (5)	−0.0028 (5)
C8	0.0653 (9)	0.0450 (8)	0.0415 (8)	−0.0034 (7)	0.0031 (7)	0.0058 (6)
C9	0.0530 (8)	0.0546 (8)	0.0434 (8)	−0.0092 (7)	0.0091 (6)	0.0047 (6)
C10	0.0423 (7)	0.0564 (8)	0.0411 (7)	0.0032 (6)	0.0089 (6)	0.0012 (6)
C11	0.0394 (7)	0.0579 (8)	0.0437 (7)	0.0024 (6)	0.0093 (6)	0.0043 (6)
C12	0.0568 (9)	0.0616 (10)	0.0538 (9)	0.0108 (7)	0.0027 (7)	−0.0021 (7)
C13	0.0722 (11)	0.0751 (12)	0.0563 (10)	0.0039 (9)	−0.0016 (8)	−0.0111 (8)
C14	0.0600 (10)	0.0895 (13)	0.0571 (10)	0.0083 (9)	−0.0107 (8)	0.0010 (9)
C15	0.0574 (10)	0.0786 (12)	0.0652 (11)	0.0192 (8)	−0.0023 (8)	0.0061 (9)
C16	0.0512 (9)	0.0610 (9)	0.0530 (9)	0.0082 (7)	0.0054 (7)	0.0001 (7)
C17	0.0393 (7)	0.0417 (7)	0.0363 (7)	0.0023 (5)	0.0053 (5)	0.0026 (5)
C18	0.0559 (8)	0.0424 (7)	0.0341 (7)	−0.0039 (6)	0.0063 (6)	0.0067 (5)
C19	0.0970 (13)	0.0553 (9)	0.0408 (8)	−0.0065 (8)	0.0192 (8)	−0.0005 (7)
C20	0.0696 (10)	0.0620 (10)	0.0539 (9)	0.0065 (8)	−0.0070 (8)	0.0078 (8)
C21	0.0638 (10)	0.0706 (11)	0.0528 (9)	−0.0185 (8)	0.0089 (7)	0.0080 (8)

Geometric parameters (Å, º) top

O1—C17	1.2166 (16)	C10—H10A	1.0000
O2—C17	1.3479 (15)	C11—C16	1.384 (2)
O2—C18	1.4759 (15)	C11—C12	1.386 (2)
N1—C17	1.3474 (16)	C12—C13	1.382 (2)
N1—C1	1.4613 (16)	C12—H12A	0.9500
N1—H1A	0.8800	C13—C14	1.373 (3)
C1—C2	1.5208 (18)	C13—H13A	0.9500
C1—C10	1.5525 (18)	C14—C15	1.373 (3)
C1—H1B	1.0000	C14—H14A	0.9500
C2—C3	1.3880 (19)	C15—C16	1.382 (2)
C2—C7	1.3954 (18)	C15—H15A	0.9500
C3—C4	1.381 (2)	C16—H16A	0.9500
C3—H3A	0.9500	C18—C19	1.513 (2)
C4—C5	1.375 (2)	C18—C21	1.516 (2)
C4—H4A	0.9500	C18—C20	1.519 (2)
C5—C6	1.376 (2)	C19—H19A	0.9800
C5—H5A	0.9500	C19—H19B	0.9800
C6—C7	1.3963 (19)	C19—H19C	0.9800
C6—H6A	0.9500	C20—H20A	0.9800
C7—C8	1.463 (2)	C20—H20B	0.9800
C8—C9	1.329 (2)	C20—H20C	0.9800
C8—H8A	0.9500	C21—H21A	0.9800
C9—C10	1.502 (2)	C21—H21B	0.9800
C9—H9A	0.9500	C21—H21C	0.9800
C10—C11	1.517 (2)

C17—O2—C18	120.23 (10)	C13—C12—C11	121.11 (15)
C17—N1—C1	120.15 (11)	C13—C12—H12A	119.4
C17—N1—H1A	119.9	C11—C12—H12A	119.4
C1—N1—H1A	119.9	C14—C13—C12	120.40 (17)
N1—C1—C2	110.33 (10)	C14—C13—H13A	119.8
N1—C1—C10	113.59 (11)	C12—C13—H13A	119.8
C2—C1—C10	113.14 (10)	C13—C14—C15	119.27 (16)
N1—C1—H1B	106.4	C13—C14—H14A	120.4
C2—C1—H1B	106.4	C15—C14—H14A	120.4
C10—C1—H1B	106.4	C14—C15—C16	120.35 (16)
C3—C2—C7	119.23 (12)	C14—C15—H15A	119.8
C3—C2—C1	119.50 (12)	C16—C15—H15A	119.8
C7—C2—C1	121.21 (12)	C15—C16—C11	121.21 (15)
C4—C3—C2	121.09 (14)	C15—C16—H16A	119.4
C4—C3—H3A	119.5	C11—C16—H16A	119.4
C2—C3—H3A	119.5	O1—C17—N1	124.84 (12)
C5—C4—C3	119.73 (14)	O1—C17—O2	125.20 (12)
C5—C4—H4A	120.1	N1—C17—O2	109.95 (11)
C3—C4—H4A	120.1	O2—C18—C19	102.18 (11)
C4—C5—C6	120.03 (14)	O2—C18—C21	110.05 (11)
C4—C5—H5A	120.0	C19—C18—C21	110.78 (13)
C6—C5—H5A	120.0	O2—C18—C20	110.34 (11)
C5—C6—C7	120.99 (14)	C19—C18—C20	110.56 (13)
C5—C6—H6A	119.5	C21—C18—C20	112.45 (13)
C7—C6—H6A	119.5	C18—C19—H19A	109.5
C2—C7—C6	118.91 (13)	C18—C19—H19B	109.5
C2—C7—C8	119.49 (12)	H19A—C19—H19B	109.5
C6—C7—C8	121.60 (13)	C18—C19—H19C	109.5
C9—C8—C7	122.09 (13)	H19A—C19—H19C	109.5
C9—C8—H8A	119.0	H19B—C19—H19C	109.5
C7—C8—H8A	119.0	C18—C20—H20A	109.5
C8—C9—C10	122.52 (13)	C18—C20—H20B	109.5
C8—C9—H9A	118.7	H20A—C20—H20B	109.5
C10—C9—H9A	118.7	C18—C20—H20C	109.5
C9—C10—C11	112.57 (12)	H20A—C20—H20C	109.5
C9—C10—C1	113.87 (11)	H20B—C20—H20C	109.5
C11—C10—C1	112.64 (11)	C18—C21—H21A	109.5
C9—C10—H10A	105.6	C18—C21—H21B	109.5
C11—C10—H10A	105.6	H21A—C21—H21B	109.5
C1—C10—H10A	105.6	C18—C21—H21C	109.5
C16—C11—C12	117.65 (14)	H21A—C21—H21C	109.5
C16—C11—C10	121.01 (13)	H21B—C21—H21C	109.5
C12—C11—C10	121.34 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	2.48	3.3517 (15)	169

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₃NO₂
M_r	321.40
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	29.4222 (10), 5.4655 (1), 21.7842 (7)
β (°)	95.4570 (13)
V (Å³)	3487.18 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.46 × 0.22 × 0.18

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.824, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	12640, 3901, 2869
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.02
No. of reflections	3901
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: COLLECT (Nonius, 2003), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SIR92 (Altomare et al., 1994), SHELXTL/PC (Sheldrick, 2001), SHELXTL/PC.