August 02, 2011 · Supporting Infomation BINOL-Al Catalysed Asymmetic Cyclization and...
Transcript of August 02, 2011 · Supporting Infomation BINOL-Al Catalysed Asymmetic Cyclization and...
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Supporting Infomation
BINOL-Al Catalysed Asymmetic Cyclization and
Amplification: Preparation of Optically Active Menthol
Analogs
Hisanori Itoha,b, Hironori Maedaa, Shinya Yamadaa, Yoji Horia,*
Takashi Minob,*, Masami Sakamotob
a Taksasago International Corporation, 4-11, Nishi-Yawata 1-Chome, Hiratsuka
City, Kanagawa 254-0073, Japan
b Department of Applied Chemistry and Biotechnology, Graduate School of
Engineering, Chiba University, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
S1
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015
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Table of Contents
Table S1 S3
ESI-MS analysis of (R)-BINOL ((R)-4a)-Al S4
NMR data of products S5
GC data of products S15
S2
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Table S1. Asymmetric Amplification on Asymmetric cyclization of 3-methylcitronellal (1) by BINOL-Al catalyst
CHO Et3Al (5 mol %),BINOL (4a) (9 mol %)
DCM, 0-10 °C, 19 h OH
(-)-trans-21
OH
(+)-trans-2
or
Entry BINOL (4a) ee of 4a (%) Conv. (%)a ee of trans-2 (%) a,b
1 (R)-4a 10 83 17(-)23
(R)-4a(R)-4a
3040
9097
49(-)52(-)
4 (S)-4a 40 86 53(+)5 (R)-4a 50 92 65(-)67
(R)-4a(R)-4a
6080
9399
66(-)83(-)
89
(S)-4a(R)-4a
80100
9498
81(+)89(-)
10 (S)-4a 100 94 90(+)aDetermined by GC analysis.
bOptical rotation of trans-2 are shown in parentheses.
S3
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ESI-MS analysis of (R)-BINOL ((R)-4a)-Al
S4
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NMR data of products
(-)-(1R,2S)-5,5-Dimethyl-2-(prop-1-en-2-yl)cyclohexanol ((-)-trans-5-methylisopulegol) ((-)-trans-2) (Table 2, entry 3)
S5
OH
(-)-trans-2
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S6
OH
(-)-trans-2
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(+)-(1R,2S)-5,5-Dimethyl-2-(prop-1-en-2-yl)cyclohexanol ((+)-trans-5-methylisopulegol) ((+)-trans-2) (Table 2, entry 4)
S7
OH
(+)-trans-2
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S8
OH
(+)-trans-2
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(-)-(1R,2S)-5,5-Dimethyl-2-(E-6-methylhepta-2,5-dien-2-yl)cyclohexanol ((-)-trans-6) (Table 2, entry 5)
S9
OH
(-)-trans-6
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S10
OH
(-)-trans-6
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(-)-(1R,2S)-5,5-Dimethyl-2-(E-6-methylhepta-2,5-dien-2-yl)cyclohexanol ((-)-trans-6), (-)- (1R,2S)-5,5-dimethyl-2-(6-methylhepta-1,5-dien-2-yl)cyclohexanol ((-)-trans-7) (E/Z = 64/36) (Table 2, entry 6)
S11
OHOH
(-)-trans-6 (-)-trans-7
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S12
OHOH
(-)-trans-6 (-)-trans-7
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(-)-(1R,2S)-2-Isopropyl-5,5-dimethylcyclohexanol ((-)-trans-5-methylmenthol) ((-)-trans-13) (Scheme 1)
S13
OH
(-)-trans-13
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S14
OH
(-)-trans-13
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GC data of products
(-)-(1R,2S)-5,5-Dimethyl-2-(prop-1-en-2-yl)cyclohexanol ((-)-trans-5-methylisopulegol) ((-)-trans-2) (Table 2, entry 3)
S15
trans-2
(+)-trans-2
(-)-trans-2
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(+)-(1R,2S)-5,5-Dimethyl-2-(prop-1-en-2-yl)cyclohexanol ((+)-trans-5-methylisopulegol) ((+)-trans-2) (Table 2, entry 4)
S16
trans-2
(-)-trans-2
(+)-trans-2
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(+)-(1R,2S)-5,5-Dimethyl-2-(prop-1-en-2-yl)cyclohexanol by (R)-BINOL-Zn ((+)-trans-5-methylisopulegol) ((+)-trans-2) (Table 1, entry 10)
S17
trans-2
(-)-trans-2
(+)-trans-2
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(-)-(1R,2S)-5,5-Dimethyl-2-(E-6-methylhepta-2,5-dien-2-yl)cyclohexanol) ((-)-trans-6) (Table 2, entry 5)
S18
trans-6
(-)-trans-6
(+)-trans-6
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(-)-(1R,2S)-5,5-Dimethyl-2-(E-6-methylhepta-2,5-dien-2-yl)cyclohexanol ((-)-trans-6), (-)- (1R,2S)-5,5-dimethyl-2-(6-methylhepta-1,5-dien-2-yl)cyclohexanol ((-)-trans-7) (E/Z = 64/36) (Table 2, entry 6)
S19
trans-6
trans-7
(+)-trans-6(-)-trans-7
(+)-trans-7
(-)-trans-6
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(+)-(1R,2S)-5,5-Dimethyl-2-(E-6-methylhepta-2,5-dien-2-yl)cyclohexanol ((+)-trans-6), (+)- (1R,2S)-5,5-dimethyl-2-(6-methylhepta-1,5-dien-2-yl)cyclohexanol ((+)-trans-7) by (R)-BINOL-Zn (E/Z = 62 / 38) S1
S20
trans-6
trans-7
(+)-trans-6
(-)-trans-7
(+)-trans-7
(-)-trans-6
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(-)-(1R,2S)-2-Isopropyl-5,5-dimethylcyclohexanol ((-)-trans-5-methylmenthol) ((-)-trans-13) (Scheme 1)
S21
(-)-trans-13
(+)-trans-13
trans-13
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S1 (a) S. Sakane, K. Maruoka and H. Yamamoto, Tetrahedron Lett., 1985, 5535; (b) S. Sakane, K. Maruoka and H. Yamamoto, Tetrahedron, 1986, 2203.
S22