Prev. Article Next Article Table of Contents

Article

Selective Ortho and Benzylic Functionalization of Secondary and Tertiary p-Tolylsulfonamides. Ipso-Bromo Desilylation and Suzuki Cross-Coupling Reactions

Supporting Info

Stephen L. MacNeil,^†^§ O. B. Familoni,^‡ and Victor Snieckus*^†^§

Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, University of Waterloo, Waterloo, ON, Canada, N2L 3G1, Department of Chemistry, Queen's University, Kingston, ON, Canada, K7L 3N6, and Department of Chemistry, University of Lagos, Akoka-Yaba, Lagos, Nigeria

J. Org. Chem., 2001, 66 (11), pp 3662–3670

DOI: 10.1021/jo001402s

Publication Date (Web): May 10, 2001

†

University of Waterloo.

Present address: Queen's University.

‡

University of Lagos.

To whom correspondence should be addressed. Fax: (613) 533-2837.

, snieckus@chem.queensu.ca

Abstract

Kinetic vs thermodynamic deprotonation studies on secondary and tertiary sulfonamides 1 and 2 using n-BuLi have been carried out. While both 1 and 2 show kinetic ortho-metalation, thermodynamic conditions lead to ortho and benzylic deprotonation, respectively (Figures 1 and 2). Metalation of 1 using the n-BuLi/KOtBu superbase led to regioselective benzylic metalation (Figure 4); LDA deprotonation was also briefly explored. Application of the developed conditions allows the synthesis of diverse sulfonamide products 5a−e, 6a−e, 7a,b, and 8a−e. Ipso-bromo desilylation reactions afford sulfonamides 9a,b while Suzuki cross-coupling reactions furnish biaryl sulfonamides 11a−c.

View: Full Text HTML | Hi-Res PDF

Tools

SciFinder Links

History

Published In Issue June 01, 2001
Received September 21, 2000

Recommend & Share

Related Content

Directed Ortho Metalation−Cross Coupling Strategies. N-Cumyl Arylsulfonamides. Facile Deprotection and Expedient Route to 7- and 4,7-Substituted SaccharinsThe Journal of Organic Chemistry
- Directed Ortho Metalation−Cross Coupling Strategies. N-Cumyl Arylsulfonamides. Facile Deprotection and Expedient Route to 7- and 4,7-Substituted Saccharins
  Jérôme Blanchet, Todd Macklin, Patrick Ang, Costa Metallinos, and Victor Snieckus
  The Journal of Organic Chemistry 2007 72 (9), pp 3199–3206
  Abstract: By using the powerful N-cumylsulfonamide directed metalation group (DMG), a series of 2-substituted derivatives were prepared according to the directed ortho metalation (DoM) tactic (Table 1). Mild conditions for N-decumylation and other simple ...
  Abstract | Full Text HTML | Hi-Res PDF
Formal Synthesis of (±)-RoseophilinOrganic Letters
- Formal Synthesis of (±)-Roseophilin
  Abdallah Y. Bitar and Alison J. Frontier
  Organic Letters 2009 11 (1), pp 49–52
  Abstract: A formal synthesis of (±)-roseophilin is described. Scandium(III)-catalyzed Nazarov cyclization of 2,5-disubstituted N-tosylpyrrole 19 gives a 5,5′-fused ketopyrrole, and ansa-bridge formation via π-allyl palladium macrocyclization gives 21.
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF
Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine LigandsAccounts of Chemical Research
- Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands
  Ruben Martin and Stephen L. Buchwald
  Accounts of Chemical Research 2008 41 (11), pp 1461–1473
  Abstract: The cores of many types of polymers, ligands, natural products, and pharmaceuticals contain biaryl or substituted aromatic structures, and efficient methods of synthesizing these structures are crucial to the work of a broad spectrum of organic ...
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF

Article

Selective Ortho and Benzylic Functionalization of Secondary and Tertiary p-Tolylsulfonamides. Ipso-Bromo Desilylation and Suzuki Cross-Coupling Reactions

Abstract

Tools

SciFinder Links

History

Recommend & Share

Related Content

Directed Ortho Metalation−Cross Coupling Strategies. N-Cumyl Arylsulfonamides. Facile Deprotection and Expedient Route to 7- and 4,7-Substituted Saccharins

Formal Synthesis of (±)-Roseophilin

Palladium-Catalyzed Suzuki−Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands

Other ACS content by these authors:

JOURNALS

BOOKS

MAGAZINE

COMMUNITIES

DIRECTORIES & DATABASES