References
-
1a
Gómez Aranda V.
Barluenga J.
Aznar F.
Synthesis
1974,
504
-
1b
Aznar F.
PhD
Thesis
Zaragoza;
Spain:
1975.
- 2
Bäckvall J.-E.
Tetrahedron
Lett.
1975,
2225
- 3
Chong AO.
Oshima K.
Sharpless KB.
J.
Am. Chem. Soc.
1977,
99:
3420
-
4a
Barluenga J.
Alonso-Cires L.
Asensio G.
Synthesis
1979,
962
-
4b
Barluenga J.
Aznar F.
de Mattos MCS.
Kover WB.
García-Granda S.
Pérez-Carreño E.
J.
Org. Chem.
1991,
56:
2930
- 5
Schofield MH.
Kee TP.
Anhaus JT.
Schrock RR.
Johnson KH.
Davis WM.
Inorg.
Chem.
1991,
30:
3595
-
Catalytic racemic diamination of
functionalised olefins:
-
6a
Jeong JU.
Tao B.
Sagasser I.
Henniges H.
Sharpless KB.
J.
Am. Chem. Soc.
1998,
120:
6844
-
6b
Li G.
Wei H.-X.
Kim SH.
Carducci M.
Angew. Chem. Int. Ed.
2001,
40:
4277
-
6c
Wei H.-X.
Kim SH.
Li G.
J. Org.
Chem.
2002,
67:
4777
-
7a
Lucet D.
Le Gall T.
Mioskowski C.
Angew. Chem. Int. Ed.
1998,
37:
2580
-
7b
Noyori R.
Ohkuma T.
Angew. Chem. Int. Ed.
2001,
40:
40
-
8a
Nugent WA.
Harlow RL.
McKinney RJ.
J.
Am. Chem. Soc.
1979,
101:
7265
-
8b
Danopoulos AA.
Wilkinson G.
Hussain-Bates B.
Hursthouse MB.
J. Chem.
Soc., Dalton Trans.
1991,
269
-
9a
Kolb HC.
VanNieuwenhze MS.
Sharpless KB.
Chem.
Rev.
1994,
94:
2483
-
9b
Kolb HC.
Sharpless KB. In Transition
Metals For Organic Chemistry: Building Blocks and Fine Chemicals
Vol.
II:
Beller M.
Bolm C.
Wiley-VCH;
Weinheim:
1998.
p.219
-
9c
Kolb HC.
Sharpless KB. In Transition
Metals For Organic Chemistry: Building Blocks and Fine Chemicals
Vol.
II:
Beller M.
Bolm C.
Wiley-VCH;
Weinheim:
1998.
p.243
-
9d
Bolm C.
Hildebrand JP.
Muñiz K. In Catalytic Asymmetric Synthesis
Ojima I.
Wiley-VCH;
Weinheim:
2000.
p.299
-
9e For stoichiometric asymmetric aminohydroxylation
reactions, see also: Rubenstein H.
Svendsen JS.
Acta Chem. Scand.
1994,
48:
439
- 12 Data for crystal structure analysis
were measured on a Nonius KappaCCD diffractometer. 4a:
hexagonal, P6(1) (No.169), a = 17.7617
(2), c = 18.3872 (2) Å,
V = 5023.60 (10) Å3, Z = 6, µ = 3.847
mm-1, T = 123K, 46712 reflections, 5872
unique reflections (2θmax = 50°),
R1 = 0.0273 [I> 2sigma(I)],
wR2 = 0.0613 (all data), 373 parameters and 44 restraints.
Empirical absorption correction was applied. Crystallographic data
(excluding structure factors) for the structure reported have been
deposited with the Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC-192700. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (fax:+44 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk)
-
For example:
-
13a
Barluenga J.
Montserrat JM.
Flórez J.
García-Granda S.
Martín E.
Angew. Chem., Int.
Ed. Engl.
1994,
33:
1392
-
13b
Oppolzer W.
Robbiani C.
Bättig K.
Helv.
Chim. Acta
1980,
63:
2015
-
13c
d’Angelo J.
Maddaluno J.
J. Am.
Chem. Soc.
1986,
108:
8112
- 16
Rubin AE.
Sharpless KB.
Angew. Chem., Int.
Ed. Engl.
1997,
36:
2637
-
19a
Nakamura Y.
Hirai M.
Tamotsu K.
Yonezawa Y.
Shin C.-G.
Bull. Chem. Soc. Jpn.
1995,
68:
1369
-
19b Synthesis via aminohydroxylation: Han H.
Yoon J.
Janda KD.
J. Org. Chem.
1998,
63:
2045
- 20
Corey EJ.
DaSilva JP.
Virgil S.
Yuen P.-W.
Connell RD.
J.
Am. Chem. Soc.
1989,
111:
9243
10 Details on the full characterisation
of new compounds, further substrates including studies on functional
group tolerance, and X-ray structures of various racemic compounds
will be given in a full account.
11
Typical experimental
procedure for the diamination of olefins: (-)-8-Phenylmenthyl
cinnamate (181 mg, 0.5 mmol) was added to a solution of bis(N-t-butylimido)dioxo-osmium(VIII)
(183 mg, 0.5 mmol) in 5 mL of freshly distilled THF. The resulting
orange solution was stirred at r.t. for 11 h during which it turned
dark red. The solvent was removed under reduced pressure to leave
a red-brown oil which was passed through a small pad of silica gel
(hexanes-ethyl acetate, 4:1). The pure mixture of the two diastereomers
(248 mg, 0.34 mmol, 68% yield) was separated by semipreparative
HPLC (Knauer Eurospher 100CN, t-BuOCH3-n-hexane, 15:85, 14 mL/min,
254 nm). Retention times: 12.9 min for 4b and
15.6 min for 4a. Selected data for the
major diastereomer 4a: 1H
NMR (300 MHz, benzene-d
6,
25 °C): δ = 0.79 (d, J = 6.4
Hz, 3 H), 0.80-0.95 (m, 4 H), 1.08 (s, 3 H), 1.18 (s, 9
H), 1.19 (s, 9 H), 1.22 (s, 3 H), 1.43-1.55 (m, 1 H), 1.60-1.71
(m, 1 H), 2.05-2.20 (m, 2 H), 3.64 (s, 1 H), 4.77 (dt, J = 4.1, 10.7 Hz, 1 H), 4.90 (s,
1 H), 6.85-6.93 (m, 1 H), 7.01-7.28 (m, 9 H). 13C
NMR (75 MHz, benzene-d
6, 25 °C): δ = 21.9,
23.8, 26.7, 29.4, 30.2, 30.9, 31.3, 34.81, 39.5, 41.8, 50.2, 66.8,
67.4, 76.4, 81.3, 84.1, 125.4, 125.7, 127.2, 127.7, 127.9, 128.3,
128.6, 171.2. MS (EI, 70 eV): m/z (%):
728 (2) [M+], 469 (17), 413 (11),
279 (39), 146 (100). HRMS: calcd for C33H49N2O4
188Os:
724.3173, found: 724.3166.
14 At present we refrain from any mechanistic
discussion. Both a [2+2] or [3+2] mechanism
[9]
might be operating. Experimental
and theoretical investigations addressing this question are underway.
15 Apparently, this way of amide formation
is not a general reaction. While it worked well for the present
purpose, preliminary reactions indicated that it is not suitable
for conventional N-alkylated α-amino
esters. In these cases, the reaction proceeds very sluggishly and
with complete racemization (K. Muñiz, unpublished results).
17
Typical experimental
procedure for LiAlH
4
reduction: Osmaimidazolidine 4b (365 mg, 0.5 mmol) was dissolved in absolute
THF (4 mL), LiAlH4 (57 mg, 1.5 mmol) was added in one
portion and the resulting mixture was stirred for 2 hours at r.t.
It was treated with methanol and water, extracted with ethyl acetate,
dried over MgSO4 and filtered over celite. The solvent
was removed under reduced pressure to leave the desired compound 9 as a colourless oil (131 mg, 0.47 mmol,
94% yield). Selected data for 9: [α]D
22 = -22
(CH2Cl2, c = 0.1). 1H
NMR (300 MHz, DMSO-d
6, 25 °C): δ = 0.93
(s, 9 H), 0.97 (s, 9 H), 3.16 (dd, J = 2.6,
10.7 Hz, 1 H), 3.19-3.42 (m, 5 H), 3.80 (d, J = 7.0 Hz, 1 H), 7.19-7.47
(m, 5 H). 13C NMR (75 MHz, DMSO-d
6, 25 °C): δ = 29.9,
30.0, 49.9, 50.4, 57.58, 58.8, 61.5, 125.9, 127.4, 128.0, 147.0.
MS (EI, 70 eV): m/z (%):
278 (3) [M+], 259 (11), 222
(37), 201 (66), 166 (49), 77 (100), 65 (95). Elemental analysis:
calcd for C17H30N2O: C 73.33; H
10.86; N 10.06; found: C 73.62; H 11.01; N 9.89.
18
Typical experimental
procedure for Os removal: Osmaimidazolidine 10b (177
mg, 0.35 mmol) was dissolved in absolute ethanol (3 mL), sodium
borohydride (30 mg, 0.79 mmol) was added in small portions and the
resulting mixture was stirred for 60 min at r.t. It was filtered
over celite and the solvent was removed under reduced pressure to
leave the desired compound 11b as a colourless
oil (89 mg, 0.31 mmol, 89% yield). Selected data for 11b: [α]D
22 = -89
(CH2Cl2, c = 0.1). 1H
NMR (300 MHz, CDCl3, 25 °C): δ = 0.87
(d, J = 7.3 Hz, 3 H), 1.16 (s,
9 H), 1.26 (s, 9 H), 1.43 (s, 9 H), 2.91 (dq, J = 7.3,
9.4 Hz, 1 H), 3.47 (d, J = 9.4
Hz, 1 H), 7.52 (br s, 1 H). 13C NMR
(75 MHz, CDCl3, 25 °C):
δ = 22.7,
28.4, 29.7, 29.7, 51.8, 51.8, 52.9, 56.9, 59.3, 171.5. MS (EI, 70
eV): m/z (%): 285 (6) [M+],
228 (17), 174 (66), 125 (49), 73 (100). Elemental analysis: calcd
for C16H35N3O: C 67.32; H 12,36;
N 14.72; found: C 66. 95; H 12.22; N 15.01.