Photocatalytic deconstructive aliphatic carbon–carbon bond cleavage and functionalization of unactivated alcohols

Adisak Thanetchaiyakup; Kek Foo Chin; Miloš Ðokić; Philip Mark Leetiong Tan; Desmond Junjie Lin; Mitch Mathiew; Xin Zhao; Jerry Zhi Xiong Heng; Daryle Jun Xiong Toh; Xue Wei Liu; Balamurugan Ramalingam; Han Sen Soo

doi:10.1016/j.checat.2023.100530

Photocatalytic deconstructive aliphatic carbon–carbon bond cleavage and functionalization of unactivated alcohols

Adisak Thanetchaiyakup, Kek Foo Chin, Miloš Ðokić, Philip Mark Leetiong Tan, Desmond Junjie Lin, Mitch Mathiew, Xin Zhao, Jerry Zhi Xiong Heng, Daryle Jun Xiong Toh, Xue Wei Liu, Balamurugan Ramalingam^*, Han Sen Soo^*

^*Corresponding author for this work

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

7 Citations (Scopus)

Abstract

Carbon–carbon (C–C) bonds are challenging to selectively cleave owing to their chemical inertness and omnipresence in organic molecules; however, they can be targeted during the late-stage modification of natural products and active pharmaceutical ingredients. Herein, we report a selective deconstructive C(sp³)–C(sp³) bond cleavage and difunctionalization of unactivated alcohols mediated by a vanadium visible-light photocatalyst under ambient temperatures and pressures. Our base metal photocatalyst operates via ligand-to-metal charge transfer followed by an inner-sphere C–C bond cleavage to generate alkyl radicals that are trapped with SOMOphiles. We achieved 10 different bond formations on 44 examples using a range of commercially sourced alcohols, including natural products and biomolecules. Our protocol can also be used for the regio- and diastereoselective cyclization to form an α-aminolactone, and for the late-stage functionalization of bioactive oligopeptides to access unnatural amino acid residues.

Original language	English
Article number	100530
Journal	Chem Catalysis
Volume	3
Issue number	3
DOIs	https://doi.org/10.1016/j.checat.2023.100530
Publication status	Published - Mar 16 2023
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2023 The Author(s)

ASJC Scopus Subject Areas

Chemistry (miscellaneous)
Physical and Theoretical Chemistry
Organic Chemistry

Keywords

aliphatic alcohol substrates
aliphatic C–C bond cleavage
base-metal photocatalysis
deconstructive functionalization
photoredox catalysis
SDG3: Good health and well-being
SDG9: Industry innovation and infrastructure
unnatural α-amino acids and oligopeptides

Access to Document

10.1016/j.checat.2023.100530

Cite this

Thanetchaiyakup, A., Chin, K. F., Ðokić, M., Tan, P. M. L., Lin, D. J., Mathiew, M., Zhao, X., Heng, J. Z. X., Toh, D. J. X., Liu, X. W., Ramalingam, B., & Soo, H. S. (2023). Photocatalytic deconstructive aliphatic carbon–carbon bond cleavage and functionalization of unactivated alcohols. Chem Catalysis, 3(3), Article 100530. https://doi.org/10.1016/j.checat.2023.100530

@article{0d19ab25918843e18a3eb3e98e6027a0,

title = "Photocatalytic deconstructive aliphatic carbon–carbon bond cleavage and functionalization of unactivated alcohols",

abstract = "Carbon–carbon (C–C) bonds are challenging to selectively cleave owing to their chemical inertness and omnipresence in organic molecules; however, they can be targeted during the late-stage modification of natural products and active pharmaceutical ingredients. Herein, we report a selective deconstructive C(sp3)–C(sp3) bond cleavage and difunctionalization of unactivated alcohols mediated by a vanadium visible-light photocatalyst under ambient temperatures and pressures. Our base metal photocatalyst operates via ligand-to-metal charge transfer followed by an inner-sphere C–C bond cleavage to generate alkyl radicals that are trapped with SOMOphiles. We achieved 10 different bond formations on 44 examples using a range of commercially sourced alcohols, including natural products and biomolecules. Our protocol can also be used for the regio- and diastereoselective cyclization to form an α-aminolactone, and for the late-stage functionalization of bioactive oligopeptides to access unnatural amino acid residues.",

keywords = "aliphatic alcohol substrates, aliphatic C–C bond cleavage, base-metal photocatalysis, deconstructive functionalization, photoredox catalysis, SDG3: Good health and well-being, SDG9: Industry innovation and infrastructure, unnatural α-amino acids and oligopeptides",

author = "Adisak Thanetchaiyakup and Chin, \{Kek Foo\} and Milo{\v s} {\DH}oki{\'c} and Tan, \{Philip Mark Leetiong\} and Lin, \{Desmond Junjie\} and Mitch Mathiew and Xin Zhao and Heng, \{Jerry Zhi Xiong\} and Toh, \{Daryle Jun Xiong\} and Liu, \{Xue Wei\} and Balamurugan Ramalingam and Soo, \{Han Sen\}",

note = "Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = mar,

day = "16",

doi = "10.1016/j.checat.2023.100530",

language = "English",

volume = "3",

journal = "Chem Catalysis",

issn = "2667-1107",

publisher = "Cell Press",

number = "3",

}

TY - JOUR

T1 - Photocatalytic deconstructive aliphatic carbon–carbon bond cleavage and functionalization of unactivated alcohols

AU - Thanetchaiyakup, Adisak

AU - Chin, Kek Foo

AU - Ðokić, Miloš

AU - Tan, Philip Mark Leetiong

AU - Lin, Desmond Junjie

AU - Mathiew, Mitch

AU - Zhao, Xin

AU - Heng, Jerry Zhi Xiong

AU - Toh, Daryle Jun Xiong

AU - Liu, Xue Wei

AU - Ramalingam, Balamurugan

AU - Soo, Han Sen

PY - 2023/3/16

Y1 - 2023/3/16

N2 - Carbon–carbon (C–C) bonds are challenging to selectively cleave owing to their chemical inertness and omnipresence in organic molecules; however, they can be targeted during the late-stage modification of natural products and active pharmaceutical ingredients. Herein, we report a selective deconstructive C(sp3)–C(sp3) bond cleavage and difunctionalization of unactivated alcohols mediated by a vanadium visible-light photocatalyst under ambient temperatures and pressures. Our base metal photocatalyst operates via ligand-to-metal charge transfer followed by an inner-sphere C–C bond cleavage to generate alkyl radicals that are trapped with SOMOphiles. We achieved 10 different bond formations on 44 examples using a range of commercially sourced alcohols, including natural products and biomolecules. Our protocol can also be used for the regio- and diastereoselective cyclization to form an α-aminolactone, and for the late-stage functionalization of bioactive oligopeptides to access unnatural amino acid residues.

AB - Carbon–carbon (C–C) bonds are challenging to selectively cleave owing to their chemical inertness and omnipresence in organic molecules; however, they can be targeted during the late-stage modification of natural products and active pharmaceutical ingredients. Herein, we report a selective deconstructive C(sp3)–C(sp3) bond cleavage and difunctionalization of unactivated alcohols mediated by a vanadium visible-light photocatalyst under ambient temperatures and pressures. Our base metal photocatalyst operates via ligand-to-metal charge transfer followed by an inner-sphere C–C bond cleavage to generate alkyl radicals that are trapped with SOMOphiles. We achieved 10 different bond formations on 44 examples using a range of commercially sourced alcohols, including natural products and biomolecules. Our protocol can also be used for the regio- and diastereoselective cyclization to form an α-aminolactone, and for the late-stage functionalization of bioactive oligopeptides to access unnatural amino acid residues.

KW - aliphatic alcohol substrates

KW - aliphatic C–C bond cleavage

KW - base-metal photocatalysis

KW - deconstructive functionalization

KW - photoredox catalysis

KW - SDG3: Good health and well-being

KW - SDG9: Industry innovation and infrastructure

KW - unnatural α-amino acids and oligopeptides

UR - http://www.scopus.com/inward/record.url?scp=85149909541&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85149909541&partnerID=8YFLogxK

U2 - 10.1016/j.checat.2023.100530

DO - 10.1016/j.checat.2023.100530

M3 - Article

AN - SCOPUS:85149909541

SN - 2667-1107

VL - 3

JO - Chem Catalysis

JF - Chem Catalysis

IS - 3

M1 - 100530

ER -

Photocatalytic deconstructive aliphatic carbon–carbon bond cleavage and functionalization of unactivated alcohols

Abstract

Bibliographical note

ASJC Scopus Subject Areas

Keywords

Access to Document

Other files and links

Fingerprint

Cite this