Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates

Hisanori Nambu; Mayuka Hikime; Janagiraman Krishnamurthi; Megumi Kamiya; Naoyuki Shimada; Shunichi Hashimoto

doi:10.1016/j.tetlet.2009.03.142

Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates

Hisanori Nambu, Mayuka Hikime, Janagiraman Krishnamurthi, Megumi Kamiya, Naoyuki Shimada, Shunichi Hashimoto^*

^*Corresponding author for this work

Synthetic and Biomolecular Organic Chemistry

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56 Scopus citations

Abstract

This Letter describes asymmetric tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reaction of diazo imides containing a tethered indole catalyzed by chiral dirhodium(II) carboxylates as an approach to the pentacyclic skeleton of Aspidosperma alkaloids. The cycloaddition of carbonyl ylides derived from indolyl-substituted 2-diazo-5-imido-3-ketoesters under the influence of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh₂(S-TCPTTL)₄, provides cycloadducts in moderate yields and enantioselectivities of up to 66% ee as well as with perfect endo diastereoselectivity. This is the first example of asymmetric induction in an intramolecular cycloaddition of a carbonyl ylide across an indolyl π-bond.

Original language	English
Pages (from-to)	3675-3678
Number of pages	4
Journal	Tetrahedron Letters
Volume	50
Issue number	26
DOIs	https://doi.org/10.1016/j.tetlet.2009.03.142
State	Published - 2009/07/01

Keywords

1,3-Dipolar cycloadditions
Carbonyl ylides
Chiral dirhodium(II) carboxylates
Vindorosine

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2009.03.142

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Nambu, H., Hikime, M., Krishnamurthi, J., Kamiya, M., Shimada, N., & Hashimoto, S. (2009). Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates. Tetrahedron Letters, 50(26), 3675-3678. https://doi.org/10.1016/j.tetlet.2009.03.142

@article{e945ae80387e41458c1fac9da638f0c2,

title = "Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates",

abstract = "This Letter describes asymmetric tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reaction of diazo imides containing a tethered indole catalyzed by chiral dirhodium(II) carboxylates as an approach to the pentacyclic skeleton of Aspidosperma alkaloids. The cycloaddition of carbonyl ylides derived from indolyl-substituted 2-diazo-5-imido-3-ketoesters under the influence of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh2(S-TCPTTL)4, provides cycloadducts in moderate yields and enantioselectivities of up to 66% ee as well as with perfect endo diastereoselectivity. This is the first example of asymmetric induction in an intramolecular cycloaddition of a carbonyl ylide across an indolyl π-bond.",

keywords = "1,3-Dipolar cycloadditions, Carbonyl ylides, Chiral dirhodium(II) carboxylates, Vindorosine",

author = "Hisanori Nambu and Mayuka Hikime and Janagiraman Krishnamurthi and Megumi Kamiya and Naoyuki Shimada and Shunichi Hashimoto",

note = "Funding Information: This research was supported, in part, by a Grant-in-Aid for Scientific Research on Priority Areas 18032002 from the Ministry of Education, Culture, Sports, Science and Technology (MEXT). J.K. thanks the Japan Society for the Promotion of Science (JSPS) for postdoctoral fellowships. We thank S. Oka, M. Kiuchi, and T. Hirose of the Center for Instrumental Analysis at Hokkaido University for mass measurements and elemental analysis. ",

year = "2009",

month = jul,

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doi = "10.1016/j.tetlet.2009.03.142",

language = "英語",

volume = "50",

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Nambu, H, Hikime, M, Krishnamurthi, J, Kamiya, M, Shimada, N & Hashimoto, S 2009, 'Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates', Tetrahedron Letters, vol. 50, no. 26, pp. 3675-3678. https://doi.org/10.1016/j.tetlet.2009.03.142

Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates. / Nambu, Hisanori; Hikime, Mayuka; Krishnamurthi, Janagiraman et al.
In: Tetrahedron Letters, Vol. 50, No. 26, 01.07.2009, p. 3675-3678.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates

AU - Nambu, Hisanori

AU - Hikime, Mayuka

AU - Krishnamurthi, Janagiraman

AU - Kamiya, Megumi

AU - Shimada, Naoyuki

AU - Hashimoto, Shunichi

N1 - Funding Information: This research was supported, in part, by a Grant-in-Aid for Scientific Research on Priority Areas 18032002 from the Ministry of Education, Culture, Sports, Science and Technology (MEXT). J.K. thanks the Japan Society for the Promotion of Science (JSPS) for postdoctoral fellowships. We thank S. Oka, M. Kiuchi, and T. Hirose of the Center for Instrumental Analysis at Hokkaido University for mass measurements and elemental analysis.

PY - 2009/7/1

Y1 - 2009/7/1

N2 - This Letter describes asymmetric tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reaction of diazo imides containing a tethered indole catalyzed by chiral dirhodium(II) carboxylates as an approach to the pentacyclic skeleton of Aspidosperma alkaloids. The cycloaddition of carbonyl ylides derived from indolyl-substituted 2-diazo-5-imido-3-ketoesters under the influence of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh2(S-TCPTTL)4, provides cycloadducts in moderate yields and enantioselectivities of up to 66% ee as well as with perfect endo diastereoselectivity. This is the first example of asymmetric induction in an intramolecular cycloaddition of a carbonyl ylide across an indolyl π-bond.

AB - This Letter describes asymmetric tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reaction of diazo imides containing a tethered indole catalyzed by chiral dirhodium(II) carboxylates as an approach to the pentacyclic skeleton of Aspidosperma alkaloids. The cycloaddition of carbonyl ylides derived from indolyl-substituted 2-diazo-5-imido-3-ketoesters under the influence of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh2(S-TCPTTL)4, provides cycloadducts in moderate yields and enantioselectivities of up to 66% ee as well as with perfect endo diastereoselectivity. This is the first example of asymmetric induction in an intramolecular cycloaddition of a carbonyl ylide across an indolyl π-bond.

KW - 1,3-Dipolar cycloadditions

KW - Carbonyl ylides

KW - Chiral dirhodium(II) carboxylates

KW - Vindorosine

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U2 - 10.1016/j.tetlet.2009.03.142

DO - 10.1016/j.tetlet.2009.03.142

M3 - 学術論文

AN - SCOPUS:65549146503

SN - 0040-4039

VL - 50

SP - 3675

EP - 3678

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 26

ER -

Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates

Abstract

Keywords

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